Propargylether derivatives, a process for their preparation and their use for controlling phytopathogenic microorganisms

ABSTRACT

The invention relates to 4-propargyloxy-benzyl dervatives of the general formula (I) including the optical isomers thereof and mixtures of such isomers, wherein R 1  is hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl or optionally substituted aryl; R 2 , R 3 , R 5 , R 6 , and R 7  are each independently of each other hydrogen or optionally substituted alkyl; R 4  is optionally substituted alkyl; X is O or N—R 7 ; and R 8  is a group R 9  is optionally substituted aryl or optionally substituted heteroaryl; R 10  and R 11 , are each independently hydrogen, optionally substituted alkyl, optionally substituted alkenyl or optionally substituted alkynyl; R 12  is optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted aryl or optionally substituted heteroaryl; R 13  is hydrogen or optionally substituted alkyl, alkenyl or alkynyl; and R 14  is optionally substituted alkyl or optionally substituted amino. These compounds possess useful plant protecting properties and may advantageously be employed in agricultural practice for controlling or preventing the infestation of plants by phytopathogenic microorganisms, especially fungi.

The present invention relates to novel propargylether derivatives offormula I below. It relates to the preparation of those substances andto agrochemical compositions comprising at least one of those compoundsas active ingredient. The invention relates also to the preparation ofthe said compositions and to the use of the compounds or of thecompositions in controlling or preventing the infestation of plants byphytopathogenic microorganisms, especially fungi.

Certain amino acid carbamates, mandelic acid derivatives and alkoximinoacid derivatives have been proposed for controlling plant-destructivefungi, (for example, in EP-A-398072, WO 94/29267 and WO 96/17840). Theaction of those preparations is not, however, satisfactory in allaspects of agricultural needs. Surprisingly, with the compound structureof formula I, new kinds of microbicides having a high level of activityhave been found.

The invention relates to propargylether derivatives of the generalformula I

including the optical isomers thereof and mixtures of such isomers,whereinR₁ is hydrogen, optionally substituted alkyl, optionally substitutedcycloalkyl or optionally substituted aryl;

R₂, R₃, R₅, R₆, and R₇ are each independently of each other hydrogen oroptionally substituted alkyl;

R₄ is optionally substituted alkyl;

X is O or N—R₇; and

R₈ is a group

R₉ is optionally substituted aryl or optionally substituted heteroaryl;R₁₀ and R₁₁, are each independently hydrogen, optionally substitutedalkyl, optionally substituted alkenyl or optionally substituted alkynyl;R₁₂ is optionally substituted alkyl, optionally substituted cycloalkyl,optionally substituted aryl or optionally substituted heteroaryl;R₁₃ is hydrogen or optionally substituted alkyl, alkenyl or alkynyl; andR₁₄ is optionally substituted alkyl or optionally substituted amino.In the above definition aryl includes aromatic hydrocarbon rings likephenyl, naphthyl, anthracenyl, phenanthrenyl, with phenyl beingpreferred.Heteroaryl stands for aromatic ring systems comprising mono-, bi- ortricyclic systems wherein at least one oxygen, nitrogen or sulfur atomis present as a ring member. Typically heteroaryl comprises 1 to 4identical or different heteroatoms selected from nitrogen, oxygen andsulfur, wherein the number of oxygen and sulfuratoms normally does notexceed one. Examples are furyl, thienyl, pyrrolyl, imidazolyl,pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl,thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl,pyrazinyl, triazinyl, tetrazinyl, indolyl, benzothiophenyl,benzofuranyl, benzimidazolyl, indazolyl, benzotriazolyl, benzothiazolyl,benzoxazolyl, quinolinyl, isoquinolinyl, phthalazinyl, quinoxalinyl,quinazolinyl, cinnolinyl and naphthyridinyl.The above aryl and heteroaryl groups may carry one or more identical ordifferent substituents. Normally not more than three substituents arepresent at the same time. Examples of substituents of aryl or heteroarylgroups are: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkyl-alkyl,phenyl and phenyl-alkyl, it being possible in turn for all of thepreceding groups to carry one or more identical or different halogenatoms; alkoxy; alkenyloxy; alkynyloxy; alkoxyalkyl; haloalkoxy,alkylthio; haloalkylthio; alkylsulfonyl; formyl; alkanoyl; hydroxy;halogen; cyano; nitro; amino; alkylamino; dialkylamino; carboxyl;alkoxycarbonyl; alkenyloxycarbonyl; alkynyloxycarbonyl.

Optionally substituted alkyl, alkenyl, alkynyl or cycloalkyl groups maycarry one or more substituents selected from halogen, alkyl, alkoxy,alkylthio, nitro, cyano, hydroxy, mercapto, alkylcarbonyl oralkoxycarbonyl. Preferably, the number of substituents is no more thanthree with the exception of halogen, where the alkyl groups may beperhalogenated. In the above definitions “halogen” or the prefix “halo”includes fluorine, chlorine, bromine and iodine.

The alkyl, alkenyl and alkynyl radicals may be straight-chain orbranched. This applies also to the alkyl, alkenyl or alkynyl parts ofother alkyl-, alkenyl- or alkynyl-containing groups.

Depending upon the number of carbon atoms mentioned, alkyl on its own oras part of another substituent is to be understood as being, forexample, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,nonyl, decyl, undecyl, dodecyl and the isomers thereof, for exampleisopropyl, isobutyl, tert-butyl or sec-butyl, isopentyl or tert-pentyl.

Cycloalkyl is, depending upon the number of carbon atoms mentioned,cyclopropyl, cyclo-butyl, cyclopentyl, cyclohexyl, cycloheptyl orcyclooctyl.

Depending upon the number of carbon atoms mentioned, alkenyl as a groupor as a structural element of other groups is to be understood as being,for example, ethenyl, allyl, 1-propenyl, buten-2-yl, buten-3-yl,penten-1-yl, penten-3-yl, hexen-1-yl, 4-methyl-3-pentenyl or4-methyl-3-hexenyl.

Alkynyl as a group or as a structural element of other groups is, forexample, ethynyl, propyn-1-yl (—CH₂—C)≡CH), prop-2-ynyl (—C(—CH₃)≡CH),butyn-1-yl (—CH₂—CH₂-C≡CH), butyn-2-yl (—CH₂≡C—C—CH₃),1-methyl-2-butynyl (—CH(CH₃)—C≡C—CH₃), hexyn-1-yl (-[CH₂]₄—C≡CH),1-ethyl-2-butynyl (—CH(CH₂—CH₃)—C≡C—CH₃), or octyn-1-yl.

A haloalkyl group may contain one or more (identical or different)halogen atoms, and for example may stand for CH₂Cl, CHCl₂, CCl₃, CH₂F,CHF₂, CF₃, CH₂CH₂Br, C₂Cl₅, C₂F₅, CH₂Br, CHClBr, CF₃CH₂, etc.

The presence of at least one asymmetric carbon atom in the compounds offormula I means that the compounds may occur in optically isomeric andenantiomeric forms. As a result of the presence of a possible aliphaticC═C double bond, geometric isomerism may also occur. Formula I isintended to include all those possible isomeric forms and mixturesthereof.

Preferred subgroups of compounds of formula I are those wherein

R₁ is hydrogen, alkyl, cycloalkyl, phenyl or naphthyl; phenyl andnaphthyl being optionally substituted by substituents selected from thegroup comprising alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkyl-alkyl,phenyl and phenylalkyl, where all these groups may in turn besubstituted by one or several halogens; alkoxy, alkenyloxy, alkynyloxy;alkoxy-alkyl; haloalkoxy; alkylthio; haloalkylthio; alkylsulfonyl;formyl; alkanoyl; hydroxy; halogen; cyano; nitro; amino; alkylamino;dialkylamino; carboxy; alkoxycarbonyl; alkenyloxycarbonyl; oralkynyloxycarbonyl; or

R₁ is hydrogen, C₁-C₈-alkyl, C₃-C₈-cycloalkyl, phenyl or naphthyl;phenyl and naphthyl being optionally substituted by one to threesubstituents selected from the group comprising C₁-C₈-alkyl,C₂-C₈-alkenyl, C₂-C₈-alkynyl, C₁-C₈-haloalkyl, C₁-C₈-alkoxy,C₁-C₈-haloalkoxy, C₁-C₈-alkylthio, C₁-C₈-haloalkylthio,C₁-C₈-alkylsulfonyl, halogen, cyano and nitro; or

R₁ is hydrogen, C₁-C₆-alkyl or C₃-C₆-cycloalkyl; or

R₂ and R₃ are hydrogen or C₁-C₆-alkyl; or

R₂ and R₃ are hydrogen; or

-   -   R₄ is C₁-C₆-alkyl; or

R₅ and R₆ are hydrogen or C₁-C₆-alkyl; or

R₅ and R₆ are hydrogen

-   -   X is oxygen or nitrogen; nitrogen being optionally substituted        by hydrogen or C₁-C₈-alkyl; or R₈ is C(R₉R₁₀)-OR₁₁

R₉ is aryl or heteroaryl, each optionally substituted by substituentsselected from the group comprising alkyl, alkenyl, alkynyl, cycloalkyl,cycloalkyl-alkyl, phenyl and phenylalkyl, where all these groups may besubstituted by one or several halogens; alkoxy, alkenyloxy, alkynyloxy;alkoxy-alkyl; haloalkoxy; alkylthio; haloalkylthio; alkylsulfonyl;formyl; alkanoyl; hydroxy; halogen; cyano; nitro; amino; alkylamino;dialkylamino; carboxy; alkoxycarbonyl; alkenyloxycarbonyl andalkynyloxycarbonyl; or

R₉ is phenyl, naphthyl, 1,3-biphenyl or 1,4-biphenyl, each optionallysubstituted by one to three substituents selected from the groupcomprising C₁-C₈-alkyl, C₂-C₈-alkenyl, C₂-C₈-alkynyl, C₁-C₈-haloalkyl,C₁-C₈-alkoxy, C₁-C₈-haloalkoxy, C₁-C₈-alkylthio, C₂-C₈-haloalkylthio,C₁-C₈-alkylsulfonyl, halogen, cyano, nitro and C₁-C₈-alkoxycarbonyl; or

R₉ is phenyl, naphthyl, 1,3-biphenyl or 1,4-biphenyl, each optionallysubstituted by one to three substituents selected from the groupcomprising C₀-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy,C₁-C₆-alkylthio, C₁-C₆-haloalkylthio, halogen, cyano, nitro andC₁-C₆-alkoxycarbonyl; or

R₁₀ is hydrogen, C₁-C₈-alkyl, C₁-C₈-haloalkyl, C₃-C₈-alkenyl orC₃-C₈-alkynyl; or

R₁₀ is hydrogen or C₁-C₆-alkyl; or

R₁₀ is hydrogen; or

R₁₁ is hydrogen, C₁-C₈-alkyl, C₁-C₈-haloalkyl, C₃-C₈-alkenyl orC₃-C₈-alkynyl; or

R₁₁ is hydrogen, C₁-C₈-alkyl, C₃-C₈-alkenyl or C₃-C₈-alkynyl; or

R₁₁ is hydrogen, C₁-C₆-alkyl or C₃-C₆-alkynyl; or

R₁₂ is C₁-C₈-alkyl, C₃-C₈-cycloalkyl, phenyl or naphthyl; phenyl andnaphthyl being optionally substituted by one to three substituentsselected from the group comprising C₁-C₈-alkyl, C₂-C₈-alkenyl,C₂-C₈-alkynyl, C₁-C₈-haloalkyl, C₁-C₈-alkoxy, C₁-C₈-haloalkoxy,C₁-C₈-alkylthio, C₁-C₈-haloalkylthio, C₁-C₈-alkylsulfonyl, aryl,halogen, cyano and nitro; or

R₁₂ is C₁-C₆-alkyl or C₃-C₆-cycloalkyl; or

R₁₃ is hydrogen, C₁-C₈-alkyl, C₁-C₈-haloalkyl, C₃-C₈-alkenyl orC₃-C₈-alkynyl; or

R₁₃ is hydrogen or C₁-C₆-alkyl; or

R₁₃ is hydrogen; or

R₁₄ is C₁-C₈-alkyl, C₁-C₈-haloalkyl, C₁-C₈-alkylamino orC₁-C₈-dialkylamino; or

R₁₄ is C₁-C₆-alkyl or C₁-C₆-dialkylamino.

One preferred subgroup of the compounds of formula I consists of thosecompounds wherein R₁₀ is hydrogen or alkyl,

X is oxygen, and

R₈ is —C(R₉R₁₀)—OR₁₁ and

R₁₁ is hydrogen or alkynyl; or wherein

X is oxygen,

R₈ is —C(R₁₂R₁₃)NH—SO₂—R₁₄, and

R₁₂ is alkyl or branched alkyl.

Further preferred subgroups of the compounds of formula I are thosewherein

R₁ is hydrogen, alkyl, cycloalkyl, phenyl or naphthyl; phenyl andnaphthyl being optionally substituted by substituents selected from thegroup comprising alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkyl-alkyl,phenyl and phenylalkyl, where all these groups may in turn besubstituted by one or several halogens; alkoxy; alkenyloxy; alkynyloxy;alkoxy-alkyl; haloalkoxy; alkylthio; haloalkylthio; alkylsulfonyl;formyl; alkanoyl; hydroxy; halogen; cyano; nitro; amino; alkylamino;dialkylamino; carboxy; alkoxycarbonyl; alkenyloxycarbonyl; oralkynyloxycarbonyl; and R₄ is alkyl; and R₈ is a group —C(R₉R₁₀)—OR₁₁,R₉ is aryl or heteroaryl, each optionally substituted by substituentsselected from to group comprising alkyl, alkenyl, alkynyl, cycloalkyl,cycloalkyl-alkyl, phenyl and phenylalkyl, where all these groups may besubstituted by one or several halogens; alkoxy, alkenyloxy, alkynyloxy;alkoxy-alkyl; haloalkoxy; alkylthio; haloalkylthio; alkylsulfonyl;formyl; alkanoyl; hydroxy; halogen; cyano; nitro; amino; alkylamino;dialkylamino; carboxy; alkoxycarbonyl; alkenyloxycarbonyl andalkynyloxycarbonyl; and R₁, is hydrogen; alkyl or alkynyl; or R₈ is agroup —C(R₁₂R₁₃)NH—SO₂—R₁₄, R₁₄ is alkyl or alkylamino; or wherein

R₁ is hydrogen, C₁-C₈-alkyl, C₃-C₈-cycloalkyl; and R₂, R₃, R₅ and R₆ arehydrogen; and R₄ is C₁-C₆-alkyl; and R₉ is phenyl, naphthyl,1,3-biphenyl or 1,4-biphenyl, each optionally substituted by one tothree substituents selected from the group comprising C₁-C₈-alkyl,C₂-C₈-alkenyl, C₂-C₈-alkynyl, C₁-C₈-haloalkyl, C₁-C₈-alkoxy,C₁-C₈-haloalkoxy, C₁-C₈-alkylthio, C₁-C₈-haloalkylthio,C₁-C₈-alkylsulfonyl, halogen, cyano, nitro and C₁-C₈-alkoxycarbonyl; andR₁₀ is hydrogen or C₁-C₄-alkyl; and R₁₁ is hydrogen, C₁-C₈-alkyl orC₂-C₈-alkynyl; and R₁₂ is C₁-C₈-alkyl, C₃-C₆-cycloalkyl, C₃-C₈-alkenyl,C₃-C₈-alkynyl; phenyl or benzyl wherein the phenyl and benzyl isoptionally substituted by one to three substituents selected from thegroup comprising C₁-C₈-alkyl, C₂-C₈-alkenyl, C₂-C₈-alkynyl,C₁-C₈-haloalkyl, C₁-C₆-alkoxy, C₁-C₈-haloalkoxy, C₁-C₈-alkylthio,C₁-C₈-haloalkylthio, C₁-C₈-alkylsulfonyl, halogen, cyano, nitro andC₁-C₈-alkoxycarbonyl; and R₁₃ is hydrogen or C₁-C₄-alkyl; and R₁₄ isC₁-C₆-alkyl; C₁-C₆-monoalkylamino or C₁-C₆-dialkylamino; or wherein

R₁ is hydrogen or C₁-C₆-alkyl, and R₂, R₃, R₅ and R₆ are hydrogen; andR₄ is methyl or ethyl; and R₉ is phenyl or naphthyl each optionallysubstituted by one to three substituents selected from the groupcomprising C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy,C₁-C₆-alkylthio, C₁-C₆-haloalkylthio, halogen, cyano, nitro andC₁-C₆-alkoxycarbonyl; and R₁₀ and R₁₃ are each hydrogen; and R₁₁, ishydrogen or C₂-C₆-alkynyl; and R₁₂ is C₂-C₆-alkyl or C₃-C₆-cycloalkyl;and R₁₄ is C₁-C₆-alkyl or C₁-C₆-dialkylamino.

Preferred individual compounds are:

-   2-hydroxy-N-(3-methoxy-4-prop-2-ynyloxy-benzyloxy)-2-phenyl-acetamide,-   N-(3-methoxy-4-prop-2-ynyloxy-benzyloxy)-2-phenyl-2-prop-2-ynyloxy-acetamide,-   2-hydroxy-N-(3-methoxy-4-pent-2-ynyloxy-benzyloxy)-2-phenyl-acetamide,-   N-(3-methoxy-4-pent-2-ynyloxy-benzyloxy)-2-phenyl-2-prop-2-ynyloxy-acetamide,-   2-(4-chloro-phenyl)-2-hydroxy-N-(3-methoxy-4-prop-2-ynyloxy-benzyloxy)-acetamide,-   2-(4-chloro-phenyl)-N-(3-methoxy-4-prop-2-ynyloxy-benzyloxy)-2-prop-2-ynyloxy-acetamide,-   2-(4-chloro-phenyl)-2-hydroxy-N-(3-methoxy-4-pent-2-ynyloxy-benzyloxy)-acetamide,-   2-(4-chloro-phenyl)-N-(3-methoxy-4-pent-2-ynyloxy-benzyloxy)-2-prop-2-ynyloxy-acetamide,-   2-(4-bromo-phenyl)-2-hydroxy-N-(3-methoxy-4-prop-2-ynyloxy-benzyloxy)-acetamide,-   2-(4-bromo-phenyl)-N-(3-methoxy-4-prop-2-ynyloxy-benzyloxy)-2-prop-2-ynyloxy-acetamide,-   2-(4-bromo-phenyl)-2-hydroxy-N-(3-methoxy-4-pent-2-ynyloxy-benzyloxy)-acetamide,-   2-(4-bromo-phenyl)-N-(3-methoxy-4-pent-2-ynyloxy-benzyloxy)-2-prop-2-ynyloxy-acetamide,-   2-(3,4-dichloro-phenyl)-2-hydroxy-N-(3-methoxy-4-prop-2-ynyloxy-benzyloxy)-acetamide,-   2-(3,4-dichloro-phenyl)-N-(3-methoxy-4-prop-2-ynyloxy-benzyloxy)-2-prop-2-ynyioxy-acetamide,-   2-(3,4-dichloro-phenyl)-2-hydroxy-N-(3-methoxy-4-pent-2-ynyloxy-benzyloxy)-acetamide,-   2-(3,4-dichloro-phenyl)-N-(3-methoxy-4-pent-2-ynyloxy-benzyloxy)-2-prop-2-ynyloxy-acetamide,-   (S)-2-methylsulfonylamino-N-(3-methoxy-4-prop-2-ynyloxy-benzyloxy)-3-methyl-butyramide,-   (S)-2-methylsulfonylamino-N-(3-methoxy-4-pent-2-ynyloxy-benzyloxy)-3-methyl-butyramide,-   (S)-N-{4-[3-(4-chloro-phenyl)-prop-2-ynyloxy]-3-methoxy-benzyloxy}-2-methylsulfonylamino-3-methyl-butyramide,-   (S)-2-ethylsulfonylamino-N-(3-methoxy-4-prop-2-ynyloxy-benzyloxy)-3-methyl-butyramide,-   (S)-N-(4-[3-(4-chloro-phenyl)-prop-2-ynyloxy]-3-methoxy-benzyloxy)-2-N,N′-dimethylamino-sulfonylamino-3-methyl-butyramide,-   2-(4-ethyl-phenyl)-2-hydroxy-N-(3-methoxy-4-prop-2-ynyloxy-benzyloxy)-acetamide,-   2-(4-ethyl-phenyl)-2-hydroxy-N-(3-methoxy-4-pent-2-ynyloxy-benzyloxy)-acetamide,-   (S)-2-ethylsulfonylamino-N-(3-mothoxy-4-pent-2-ynyloxy-benzyloxy)-3-methyl-butyramide,-   (S)-N-{4-[3-(4-chloro-phenyl)-prop-2-ynyloxy]-3-methoxy-benzyloxy}-2-ethanesulfonylamino-3-methyl-butyramide,-   hydroxy-phenyl-acetic acid    N′-(3-methoxy-4-prop-2-ynyloxy-benzyl)-hydrazide,-   phenyl-prop-2-ynyloxy-acetic acid    N′-(3-methoxy-4-prop-2-ynyloxy-benzyl)-hydrazide,-   hydroxy-phenyl-acetic acid    N′-(3-methoxy-4-pent-2-ynyloxy-benzyl)-hydrazide,-   phenyl-prop-2-ynyloxy-acetic acid    N′-(3-methoxy-4-pent-2-ynyloxy-benzyl)-hydrazide,-   (4-chloro-phenyl)-hydroxy-acetic acid    N′-(3-methoxy-4-prop-2-ynyloxy-benzyl)-hydrazide,-   (4-chloro-phenyl)-prop-2-ynyloxy-acetic acid    N′-(3-methoxy-4-prop-2-ynyloxy-benzyl)-hydrazide,-   (4-chloro-phenyl)-hydroxy-acetic acid    N′-(3-methoxy-4-pent-2-ynyloxy-benzyl)-hydrazide,-   (4-chloro-phenyl)-prop-2-ynyloxy-acetic acid    N′-(3-methoxy-4-pent-2-ynyloxy-benzyl)-hydrazide,-   (4-bromo-phenyl)-hydroxy-acetic acid    N′-(3-methoxy-4-prop-2-ynyloxy-benzyl)-hydrazide,-   (4-bromo-phenyl)-prop-2-ynyloxy-acetic acid    N′-(3-methoxy-4-prop-2-ynyloxy-benzyl)-hydrazide,-   (4-bromo-phenyl)-hydroxy-acetic acid    N′-(3-methoxy-4-pent-2-ynyloxy-benzyl)-hydrazide,-   (4-bromo-phenyl)-prop-2-ynyloxy-acetic acid    N′-(3-methoxy-4-pent-2-ynyloxy-benzyl)-hydrazide,-   (3,4-dichloro-phenyl)-hydroxy-acetic acid    N′-(3-methoxy-4-prop-2-ynyloxy-benzyl)-hydrazide,-   (3,4-dichloro-phenyl)-prop-2-ynyloxy-acetic acid    N′-(3-methoxy-4-prop-2-ynyloxy-benzyl)-hydrazide,-   (3,4-dichloro-phenyl)-hydroxy-acetic acid    N′-(3-methoxy-4-pent-2-ynyloxy-benzyl)-hydrazide,-   (3,4-dichloro-phenyl)-prop-2-ynyloxy-acetic acid    N′-(3-methoxy-4-pent-2-ynyloxy-benzyl)-hydrazide,-   N-{(S)-1-[N′-(3-methoxy-4-prop-2-ynyloxy-benzyl)-hydrazinocarbonyl]-2-methyl-propyl)-methylsulfonamide,-   N-{(S)-1-[N′-(3-methoxy-4-pent-2-ynyloxy-benzyl)-hydrazinocarbonyl]-2-methyl-propyl)-methylsulfonamide,-   N-[(S)-1-(N′-(4-[3-(4-chloro-phenyl)-prop-2-ynyloxy]-3-methoxy-benzyl}-hydrazinocarbonyl)-2-methyl-propyl]-methylsulfonamide,-   N-{(S)-1-[N′-(3-methoxy-4-prop-2-ynyloxy-benzyl)-hydrazinocarbonyl]-2-methyl-propyl}-ethylsulfonamide,-   N-{(S)-1-[N′-(3-methoxy-4-pent-2-ynyloxy-benzyl)-hydrazinocarbonyl]-2-methyl-propyl}-ethylsulfonamide,    and-   N-[(S)-1-(N′-[4-[3-(4-chloro-phenyl)-prop-2-ynyloxy]-3-methoxy-benzyl}-hydrazinocarbonyl]-2-methyl-propyl]-ethylsulfonamide.

The propargylether derivatives of formula I may be obtained according toone of the processes of Schemes 1 to 3:

Step A: An acid of formula II or a carboxy-activated derivative of anacid of formula II wherein R₈ is as defined for formula I is reactedwith an amino-derivative of formula III wherein R₄, R₅, R₆ and X are asdefined for formula I, optionally in the presence of a base andoptionally in the presence of an inert solvent.

Carboxy-activated derivatives of the acid of formula II for the purposeof this invention encompass all derivatives of compounds of formula IIhaving an activated carboxyl group like an acid halide, such as an acidchloride, like symmetrical or mixed anhydrides, such as mixed anhydrideswith O-alkylcarbonates, like activated esters, such asp-nitrophenylesters or N-hydroxysuccinimidesters, as well asin-situ-formed activated forms of the acid of formula II withcondensating agents, such as dicyclohexylcarbodiimide,carbonyldiimidazole, benzotriazol-1-yloxy-tris(dimethylamino)phosphoniumhexafluorophosphate, O-benzotriazol-1-ylN,N,N′,N′-bis(pentamethylene)uronium hexafluorophosphate,O-benzotriazol-1-yl N,N,N′,N′-bis(tetramethylene)uroniumhexafluorophosphate, O-benzotriazol-1-yl N,N,N′,N′-tetramethyluroniumhexafluorophosphate or benzotriazol-1-yloxy-tripyrrolidinophosphoniumhexafluorophosphate. The mixed anhydrides of the acids of the formula IImay be prepared by reaction of an acid of formula II with chloroformicacid esters like chloroformic acid alkylesters, such as ethylchloroformate or isobutyl chloroformate, optionally in the presence ofan organic or inorganic base like a tertiary amine, such astriethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidineor N-methyl-morpholine.

The present reaction is preferably performed in an inert solvent likearomatic, non-aromatic or halogenated hydrocarbons, such aschlorohydrocarbons e.g. dichloromethane or toluene; ketones e.g.acetone; esters e.g. ethyl acetate; amides e.g. N,N-dimethylformamide;nitriles e.g. acetonitrile; or ethers e.g. diethylether,tert-butyl-methylether, dioxane or tetrahydrofurane or water. It is alsopossible to use mixtures of these solvents. The reaction is performedoptionally in the presence of an organic or inorganic base like atertiary amine, e.g. triethylamine, N,N-diisopropyl-ethylamine,pyridine, N-methyl-piperidine or N-methyl-morpholine, like a metalhydroxide or a metal carbonate, preferentially an alkali hydroxide or analkali carbonate, such as lithium hydroxide, sodium hydroxide orpotassium hydroxide at temperatures ranging from −80° C. to +150° C.,preferentially at temperatures ranging from −40° C. to +40° C.

Step B: The compounds of formula I may then finally be prepared byreaction of a phenol of formula IV wherein R₄, R₅, R₆, R₈ and X are asdefined for formula I with a compound of formula V wherein R₁, R₂ and R₃are as defined for formula I and wherein Y is a leaving group like ahalide such as a chloride or bromide or a sulfonic ester such as atosylate, mesylate or triflate.

The reaction is advantageously performed in an inert solvent likearomatic, non-aromatic or halogenated hydrocarbons, such aschlorohydrocarbons e.g. dichloromethane or toluene; ketones e.g. acetoneor 2-butanone; esters e.g. ethyl acetate; ethers e.g. diethylether,tert-butyl-methylether, dioxane or tetrahydrofurane, amides e.g.dimethylformamide, nitrites e.g. acetonitrile, alcohols e.g. methanol,ethanol, isopropanol, n-butanol or tert-butanol, sulfoxides e.g.dimethylsulfoxide or water. It is also possible to use mixtures of thesesolvents. The reaction is performed optionally in the presence of anorganic or inorganic base like a tertiary amine, such as triethylamine,N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine orN-methyl-morpholine, like a metal hydroxide, a metal carbonate or ametal alkoxide, preferentially an alkali hydroxide, an alkali carbonateor an alkali alkoxide, such as lithium hydroxide, sodium hydroxide,potassium hydroxide, sodium carbonate, potassium carbonate, sodiummethoxide, potassium methoxide, sodium ethoxide, potassium ethoxide,sodium tert-butoxide or potassium tert-butoxide at temperatures rangingfrom −80° C. to +200° C., preferentially at temperatures ranging from 0°C. to +120° C.

Step C: Alternatively to the sequence of steps A and B, an acid offormula II or a carboxy-activated derivative of an acid of formula IIwherein R₈ is as defined for formula I may be reacted with anamino-derivative of formula VI wherein R₁, R₂, R₃, R₄, R₅, R₆ and X areas defined for formula I under the same conditions as defined for stepA, optionally in the presence of a base and optionally in the presenceof a diluting inert solvent.

Scheme 2:

Example for the preparation of intermediates of formula IV (wherein X isnitrogen and R₆ is hydrogen)

Step D: An acid hydrazide of formula VII wherein R₈ is as defined forformula I is reacted with a carbonyl compound of formula VIII wherein R₄and R₅ are as defined for formula I. The reaction corresponds to astandard hydrazone formation and is with advantage performed in an inertsolvent capable of forming azeotropic evaporates. The reaction mayfurther be catalyzed by the presence of a mineral acid such ashydrochloric acid or sulfuric acid or an organic acid like formic acidor acetic acid. Water is eliminated during the condensation reaction,which preferably is continuously separated from the reaction mixture byazeotropic destillation, e.g. by using a Dean-Stark trap. Suitablesolvents for this purpose include aromatic hydrocarbons like benzene,toluene and xylene or chlorinated hydrocarbons like methylene chlorideor chloroform.Step E: An acylhydrazone of formula IX wherein R₄, R₅ and R₈ are asdefined for formula I is reduced to a compound of formula IVa whereinR₄, R₅ and R₈ are as defined for formula I by reaction with reducingagents like hydrogen or hydrazine In the presence of a suitable catalystsuch as rhodium, platinum or palladium on carbon, or by reductivetransformation with a metal hydride such as sodium borohydride, sodiumcyanoborohydride or lithium aluminumhydride under conditions known perse (K. Shanker et al., Arch. Pharm. (Weinheim), 317, 890 (1984). Thehydrogenation reaction is preferably performed in a solvent like esterse.g. ethyl acetate; amides e.g. N,N-dimethylformamide; or carboxylicacids, e.g. acetic acid; the transformations with metal hydride arepreferably performed in a solvent like ethers e.g. diethylether,tert-butyl-methylether, dioxane or tetrahydrofurane; alcohols e.g.methanol or ethanol. It is also possible to use mixtures of thesesolvents. Furthermore the hydrogenation reaction can be performed atpressures between atmospheric pressure and 120 bar, preferentially atpressures ranging from 1 to 80 bar.Scheme 3:

Example for the preparation of intermediates of formula VI (X=O)

Step F: A phenol of formula X wherein R₄, R₅ and R₆ are as defined forformula I is reacted with a compound of formula V wherein R₁, R₂ and R₃are as defined for formula I and wherein Y is a leaving group like ahalide such as a chloride or bromide or a sulfonic ester such as atosylate, mesylate or triflate under the same conditions as defined forstep B in Scheme 1.Step G: An alcohol of formula XI wherein R₁, R₂, R₃, R₄, R₅ and R₆ areas defined for formula I is transformed into a compound of formula XIIwherein R₁, R₂, R₃, R₄, R₅ and R₆ are as defined for formula I andwherein Y is a leaving group like a halide such as a chloride or bromideor a sulfonic ester such as a tosylate, mesylate or triflate. Thereaction can be achieved by converting the compound of formula XI e.g.with hydrochloric acid, hydrogen bromide, phosphorus tetrabromide orthionyl chloride as reagent to a halide; or with mesyl chloride or tosylchloride as reagent to a sulfonic ester.Step H: A compound of formula XII wherein R₁, R₂, R₃, R₄, R₅ and R₆ areas defined for formula I is reacted with a compound of formula XIIIwherein R₁₅ and R₁₆ are hydrogen, halogen, methyl or part of anannelated benzene ring under conditions known per se for the formationof N-alkoxyimides (G. L. Verdine et al., J. Am. Chem. Soc., 123, 398(2001).Step I: A compound of formula XIV wherein R₁, R₂, R₃, R₄, R₅ and R₆ areas defined for formula I and R₁₅ and R₁₆ are hydrogen, halogen, methylor part of an annelated benzene ring is reacted with an aminederivative, like methylamine or butylamine or a hydrazine derivative,such as hydrazine, hydrazine hydrate or methylhydrazine under conditionsknown per se for the cleavage of N-alkoxyimides (M. P. Kirkup,Tetrahedron Lett., 30, 6809 (1989).

The compounds of formula I are oils or solids at room temperature andgenerally stable when stored at ambient temperatures in a warehouse.These compounds are distinguished from known compounds of the chemicalclass by their valuable microbicidal properties. They can be used in theagricultural sector or related fields preventively and curatively in thecontrol of phytopathogenic or plant-destructive microorganisms. Thecompounds of formula I according to the invention are distinguished atlow rates of concentration not only by outstanding microbicidal,especially fungicidal activity but also by being especially welltolerated by plants.

Surprisingly, it has now been found that the compounds of formula I havefor practical purposes a very advantageous biocidal spectrum in thecontrol of phytopathogenic microorganisms, especially fungi. Theypossess very advantageous curative and preventive properties and areused in the protection of numerous crop plants. With the compounds offormula I it is possible to inhibit or destroy phytopathogenicmicroorganisms that occur on various crops of useful plants or on partsof such plants (fruit, blossom, leaves, stems, tubers, roots), whileparts of the plants which grow later also remain protected, for example,against phytopathogenic fungi.

The novel compounds of formula I prove to be effective against specificgenera of the fungus class Fungi imperfecti (e.g. Cercospora),Basidiomycetes (e.g. Puccinia) and Ascomycetes (e.g. Erysiphe andVenturia) and especially against Oomycetes (e.g. Plasmopara,Peronospora, Pythium and Phytophthora). They therefore represent inplant protection a valuable addition to the compositions for controllingphytopathogenic fungi. The compounds of formula I can also be used asdressings for protecting seed (fruit, tubers, grains) and plant cuttingsfrom fungal infections and against phytopathogenic fungi that occur inthe soil.

The invention relates also to compositions comprising compounds offormula I as active ingredient, especially plant-protectingcompositions, and to the use thereof in the agricultural sector orrelated fields.

In addition, the present invention includes the preparation of thosecompositions, wherein the active ingredient is homogeneously mixed withone or more of the substances or groups of substances described herein.Also included is a method of treating plants which is distinguished bythe application of the novel compounds of formula I or of the novelcompositions.

Target crops to be protected within the scope of this inventioncomprise, for example, the following species of plants: cereals (wheat,barley, rye, oats, rice, maize, sorghum and related species); beet(sugar beet and fodder beet); pomes, stone fruit and soft fruit (apples,pears, plums, peaches, almonds, cherries, strawberries, raspberries andblackberries); leguminous plants (beans, lentils, peas, soybeans); oilplants (rape, mustard, poppy, olives, sunflowers, coconut, castor oilplants, cocoa beans, groundnuts); cucurbitaceae (marrows, cucumbers,melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges,lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus,cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae(avocado, cinnamon, camphor) and plants such as tobacco, nuts, coffee,sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants,and also ornamentals.

The compounds of formula I are normally used in the form of compositionsand can be applied to the area or plant to be treated simultaneously orin succession with other active ingredients. Those other activeingredients may be fertilisers, micronutrient donors or otherpreparations that influence plant growth. It is also possible to useselective herbicides or insecticides, fungicides, bactericides,nematicides, molluscicides or mixtures of several of those preparations,if desired together with further carriers, surfactants or otherapplication-promoting adjuvants customarily employed in formulationtechnology.

The compounds of formula I may be readily mixed with other fungicides inprefabricated compositions or as so-called tank-mixtures, exhibitingresulting in some cases unexpected resulting synergistic activities.

As ad-mixing components which are particularly suitable the azoles, suchas azaconazole, BAY 14120, bitertanol, bromuconazole, cyproconazole,difenoconazole, diniconazole, epoxiconazole, fenbuconazole,fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil,imibenconazole, ipconazole, metconazole, myclobutanil, pefurazoate,penconazole, pyrifenox, prochloraz, propiconazole, simeconazole,tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole,triticonazole; pyrimidinyl carbinole, such as ancymidol, fenarimol,nuarimol; 2-amino-pyrimidines, such as bupirimate, dimethirimol,ethirimol; morpholines, such as dodemorph, fenpropidine, fenpropimorph,spiroxamine, tridemorph; anilinopyrimidines, such as cyprodinil,mepanipyrim, pyrimethanil; pyrroles, such as fenpiclonil, fludioxonil;phenylamides, such as benalaxyl, R-benalayxl, furalaxyl, metalaxyl,R-metalaxyl, ofurace, oxadixyl; benzimidazoles, such as benomyl,carbendazim, debacarb, fuberidazole, thiabendazole; dicarboximides, suchas chlozolinate, dichlozoline, iprodione, myclozoline, procymidone,vinclozoline; carboxamides, such as carboxin, fenfuram, flutolanil,mepronil, oxycarboxin, thifluzamide; guanidines, such as guazatine,dodine, iminoctadine; strobilurines, such as azoxystrobin,kresoxim-methyl, metominostrobin, SSF-129, trifloxystrobin,picoxystrobin, BAS 500F (proposed name pyraclostrobin), BAS 520; HEC5725 (proposed common name fluoxastrobin), orysastrobin (proposed commonname), dithiocarbamates, such as ferbam, mancozeb, maneb, metiram,propineb, thiram, zineb, ziram; N-halomethylthiotetrahydro-phthalimides,such as captafol, captan, dichlofluanid, fluoromides, folpet,tolyfluanid; Cu-compounds, such as Bordeaux mixture, copper hydroxide,copper oxychloride, copper sulfate, cuprous oxide, mancopper,oxine-copper; nitrophenol-derivatives, such as dinocap,nitrothal-isopropyl; organo-P-derivatives, such as edifenphos,iprobenphos, isoprothiolane, phosdiphen, pyrazophos, tolclofos-methyl;various others, such as acibenzolar-S-methyl, anilazine,benthiavalicarb, blasticidin-S, chinomethionate, chloroneb,chlorothalonil, cyflufenamid, cymoxanil, dichlone, diclomezine,dicloran, diethofencarb, dimethomorph, SYP-L190 (proposed name: flumorphor flumorlin), dithianon, ethaboxam, etridiazole, famoxadone,fenamidone, fenoxanil, fentin, ferimzone, fluazinam, flusulfamide,fenhexamid, fosetyl-aluminium, hymexazol, iprovalicarb, DPX-KQ 926(proposed comon name proquinazid), JAU 6476 (proposed common nameprothioconazole), IKF-916 (cyazofamid), kasugamycin, methasulfocarb,metrafenone, boscalid (nicobifen), pencycuron, phthalide, polyoxins,probenazole, propamocarb, pyroquilon, quinoxyfen, quintozene, sulfur,triazoxide, tricyclazole, triforine, validamycin, zoxamide (RH7281).

Suitable carriers and surfactants may be solid or liquid and correspondto the substances ordinarily employed in formulation technology, such ase.g. natural or regenerated mineral substances, solvents, dispersants,wetting agents, tackifiers, thickeners, binders or fertilisers. Suchcarriers and additives are described, for example, in WO 95/30651.

A preferred method of applying a compound of formula I, or anagrochemical composition comprising at least one of those compounds, isapplication to the foliage (foliar application), the frequency and therate of application depending upon the risk of infestation by thepathogen in question. The compounds of formula I may also be applied toseed grains (coating) either by impregnating the grains with a liquidformulation of the active ingredient or by coating them with a solidformulation.

The compounds of formula I are used in unmodified form or, preferably,together with the adjuvants conventionally employed in formulationtechnology, and are for that purpose advantageously formulated in knownmanner e.g. into emulsifiable concentrates, coatable pastes, directlysprayable or dilutable solutions, dilute emulsions, wettable powders,soluble powders, dusts, granules, and by encapsulation in e.g. polymersubstances. As with the nature of the compositions, the methods ofapplication, such as spraying, atomising, dusting, scattering, coatingor pouring, are chosen in accordance with the intended objectives andthe prevailing circumstances.

Advantageous rates of application are normally from 1 g to 2 kg ofactive ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kga.i./ha, especially from 25 g to 750 g a.i./ha. When used as seeddressings, rates of from 0.001 g to 1.0 g of active ingredient per kg ofseed are advantageously used.

The formulations, i.e. the compositions, preparations or mixturescomprising the compound(s) (active ingredient(s)) of formula I and,where appropriate, a solid or liquid adjuvant, are prepared in knownmanner, e.g. by homogeneously mixing and/or grinding the activeingredient with extenders, e.g. solvents, solid carriers and, whereappropriate, surface-active compounds (surfactants).

Further surfactants customarily used in formulation technology will beknown to the person skilled in the art or can be found in the relevanttechnical literature.

The agrochemical compositions usually comprise 0.01 to 99% by weight,preferably 0.1 to 95% by weight, of a compound of formula I, 99.99 to 1%by weight, preferably 99.9 to 5% by weight, of a solid or liquidadjuvant, and 0 to 25% by weight, preferably 0.1 to 25% by weight, of asurfactant.

Whereas commercial products will preferably be formulated asconcentrates, the end user will normally employ dilute formulations.

The compositions may also comprise further ingredients, such asstabilisers, antifoams, viscosity regulators, binders and tackifiers, aswell as fertillsers or other active ingredients for obtaining specialeffects.

The Examples which follow illustrate the invention described above,without limiting the scope thereof in any way. Temperatures are given indegrees Celsius.

PREPARATION EXAMPLES Example A1.12-(4-Chloro-phenyl)-2-hydroxy-N-(3-methoxy-4-pent-2-ynyloxy-benzyloxy)-acetamide

a) (3-Methoxy-4-pent-2-ynyloxy-phenyl)-methanol

Sodium methoxide (36 ml of a 5.4 M solution in methanol, 0.20 mol) isadded to a solution of 4-hydroxymethyl-2-methoxy-phenol (25 g, 0.16 mol)in 250 ml of methanol. Pentinyl chloride (18.5 g, 0.18 mol) is added andthe mixture is heated to reflux for 4 hours. After evaporation of thesolvent, the residue is taken up in ethyl acetate and washed with waterand brine. The organic layer is dried over magnesium sulfate andevaporated. The residue is submitted to flash-chromatography on silicagel (ethyl acetate/hexane 1:2) to give(3-.methoxy-4-pent-2-ynyloxy-phenyl)-methanol as yellow oil.

¹H-NMR (CDCl₃, 300 MHz): 1.12 (t, 3H, Me), 2.20 (q, 2H, CH₂), 3.84 (s,3H, OMe), 4.58 (s, 2H, CH₂OH), 4.69 (d, 2H, OCH₂C≡C), 6.82-7.01 (m, 3H,ar).

b) 4-Chloromethyl-2-methoxy-1-tent-2-ynyloxy-benzene

A solution of (3-methoxy-4-pent-2-ynyloxy-phenyl)-methanol (27 g, 0.12mol) in 450 ml of dioxan is added dropwise to 240 ml of concentratedhydrochloric acid. The reaction mixture is stirred for 1.5 hours at roomtemperature. Subsequently it is poured on water and extracted with ethylacetate. The combined organic layer is washed with brine, dried overmagnesium sulfate and evaporated in vacuo to obtain4-chloromethyl-2-methoxy-1-pent-2-ynyloxy-benzene as yellow oil.

¹H-NMR (CDCl₃, 300 MHz): 1.11 (t, 3H, Me), 2.21 (q, 2H, CH₂), 3.88 (s,3H, OMe), 4.57 (s, 2H, CH₂Cl), 4.72 (d, 2H, OCH₂C≡C), 6.90-6.99 (m, 3H,ar).

c) 2-(3-Methoxy-4-pent-2-ynyloxy-benzyloxy)-isoindole-1,3-dione

4-Chloromethyl-2-methoxy-1-pent-2-ynyloxy-benzene (28 g, 0.12 mol) andN-hydroxyphthalimide (19.5 g, 0.12 mol) are dissolved in 180 ml ofN,N-dimethylformamide. The reaction mixture is heated to +70° C. andpotassium hydroxide (24 ml of a 5 M solution in methanol, 0.12 mol) isadded at this temperature. The reaction is stirred for 1 hour at +70°C., subsequently cooled to room temperature and poured on water. Thismixture is stirred for one further hour and filtered. The resultingcrystalls are washed with water and recrystallized from methanol/acetone(8:1) to yield2-(3-methoxy-4-pent-2-ynyloxy-benzyloxy)-isoindole-1,3-dione ascolourless crystalls.

¹H-NMR (CDCl₃, 300 MHz): 1.09 (t, 3H, Me), 2.19 (q, 2H, CH₂), 3.90 (s,3H, OMe), 4.72 (d, 2H, OCH₂C≡C), 5.18 (s, 2H, CH₂ON), 6.97-7.82 (m, 7H,ar).

d) O-(3-Methoxy-4-pent-2-ynyloxy-benzyl)-hydroxylamine

2-(3-Methoxy-4-pent-2-ynyloxy-benzyloxy)-isoindole-1,3-dione (27 g, 74mmol) is suspended in a mixture of 500 ml of methanol and 50 ml ofN,N-dimethylformamide. After heating this mixture to +60° C., hydrazinehydrate (8.5 g, 0.17 mol) is added. The reaction is stirred for 3 hoursat +60° C. and subsequently cooled down to room temperature. A mixtureof 28 ml of concentrated hydrochloric acid and 80 ml of water is addedto acidify the resulting suspension. Then it is filtered to remove aprecipitation and the solid is washed with water/methanol. The filtrateis concentrated in vacuo to one third of its original volume. Sodiumhydroxide (18 g, mol in 90 ml water) is added to the remainder and thismixture is extracted with diethyl ether. The combined organic layer iswashed with water and brine, dried over magnesium sulfate and evaporatedto give O-(3-methoxy-4-pent-2-ynyloxy-benzyl)-hydroxylamine as yellowoil.

¹H-NMR (CDCl₃, 300 MHz): 1.10 (t, 3H, Me), 2.21 (q, 2H, CH₂), 3.88 (s,3H, OMe), 4.65 (d, 2H, OCH₂C≡C), 4.73 (s, 2H, CH₂ON), 6.83-7.01 (m, 3H,ar).

O-(3-methoxy-4-pent-2-ynyloxy-benzyl)-hydroxylamine (5.0 g, 21 mmol) andN-ethyldiisopropylamine (Hünig's base, 5.5 g, 42 mmol) are dissolved in60 ml of N,N-dimethylformamide. 4-chloro-DL-mandelic acid (4.1 g, 22mmol) and (benzotriazol-1-yloxy)-tris-(dimethylamino)-phosphoniumhexafluorophosphate (BOP, Castro's reagent, 10 g, 23 mmol) are addedsuccessively and the mixture is stirred for 16 h. After pouring themixture on ice/water, it is extracted with ethyl acetate. The combinedorganic layer is washed with brine, dried over magnesium sulfate andevaporated under reduced pressure. The remaining oil is purified bychromatography on silica gel (ethyl acetate/hexane (4:6)) to obtain2-(4-chloro-phenyl)-2-hydroxy-N-(3-methoxy-4-pent-2-ynyloxy-benzyloxy)-acetamideas yellow resin.

¹H-NMR (CDCl₃, 300 MHz): 1.12 (t, 3H, Me), 2.19 (q, 2H, CH₂), 3.83 (s,3H, OMe), 4.69-4.78 (m, 4H, OCH₂C≡C, CH₂ON), 5.03 (s, 1H, CHOH),6.72-7.33 (m, 7H, ar).

According to the example A1.1 described above the compounds listed intable A1 are obtained. TABLE A1

physico-chemical No. R₁ R₈ data A1.01 4-Cl—Ph-

m.p. 99-102 A1.02 H

m.p. 142-145 A1.03 4-Cl—Ph—

m.p. 149-151 A1.04 H—

Oil A1.05 CH₃—CH₂—

m.p. 96-98 A1.06 CH₃—CH₂—

m.p. 132-133 A1.07 4-Cl—Ph—

m.p. 147-150 A1.08 H—

Oil A1.09 CH₃—CH₂—

Oil A1.10 CH₃—CH₂—

Oil A1.11 H—

Oil A1.12 CH₃—CH₂—

Oil A1.13 CH₃—CH₂—

Oil A1.14 H—

m.p. 118-120 A1.15 H—

Oil A1.16 CH₃—CH₂—

Oil A1.17 CH₃—CH₂—

Oil A1.18 H—

m.p. 125-127

Example A2.1 Hydroxy-(4-methoxy-phenyl)-acetic acidN′-(3-methoxy-4-prop-2-ynyloxy-benzyl)-hydrazide

a) Hydroxy-(4-methoxy-phenyl)-acetic acid hydrazide

To a solution of hydroxy-(4-methoxy-phenyl)-acetic acid (45 g, 0.25 mol)in 300 ml of methanol are added 30 drops of concentrated sulfuric acidat room temperature and the resulting mixture is heated to reflux for 4hours. Subsequently the mixture is cooled and evaporated in vacuo. Theremainder is taken up in water and extracted with ethyl acetate. Thecombined organic layer isn washed with brine, dried over magnesiumsulfate and evaporated. The residue, which ishydroxy-(4-methoxy-phenyl)-acetic acid methyl ester, is dissolved in 350ml of diethyl ether. Hydrazine monohydrate (47 ml, 0.95 mol) is addeddropwise at room temperature and the mixture is stirred for 1 hour. Thereaction mixture is poured on water and extracted with ethyl acetate.The combined organic layer is washed with brine, dried over magnesiumsulfate and evaporated, the remaining hydroxy-(4-methoxy-phenyl)-aceticacid hydrazide is sufficiently pure to be used directly in the nextstep.

¹H-NMR (CDCl₃, 300 MHz): 3.79 (s, 3H, OMe), 4.92 (d, 1H, CHOH), 5.91 (d,1H, OH), 6.92 (d, 2H, ar), 7.36 (d, 2H, ar).

b) Hydroxy-(4-methoxy-phenyl)-acetic acid[1-(4-hydroxy-3-methoxy-phenyl)-meth-(E)-ylidene]-hydrazide

Vanillin (23 g, 0.15 mol) is added to a solution ofhydroxy-(4-methoxy-phenyl)-acetic acid hydrazide (30 g, 0.15 mol) in 300ml of ethanol at room temperature. After heating this mixture to refluxfor 4 hours, the reaction is poured on water and extracted with ethylacetate. The combined organic layer is washed with brine, dried overmagnesium sulfate and evaporated. The residue, which ishydroxy-(4-methoxy-phenyl)-acetic acid[1-(4-hydroxy-3-methoxy-phenyl)-meth-(E)-ylidene]-hydrazide, issufficiently pure to be directly used in the next step.

¹H-NMR (CDCl₃, 300 MHz): 3.72 (s, 3H, OMe), 3.80 (s, 3H, OMe), 4.99 (s,1H, CHOH), 6.21 (d, 1H, CH═N), 6.79-7.42 (m, 7H, ar).

c) Hydroxy-(4-methoxy-phenyl)-acetic acidN′-(4-hydroxy-3-methoxy-benzyl)-hydrazide

A solution of hydroxy-(4-methoxy-phenyl)-acetic acid[1-(4-hydroxy-3-methoxy-phenyl)-meth-(E)-ylidene]-hydrazide (21 g, 63mmol) in 500 ml of ethanol is hydrogenated under atmospheric pressurewith hydrogen and a mixture of 5% of palladium on charcoal (10.5 g) ascatalyst. The reaction is stirred for 6 hours at room temperature.Subsequently, the mixture is filtered under argon and the solvent isevaporated to yield hydroxy-(4-methoxy-phenyl)-acetic acidN′-(4-hydroxy-3-methoxy-benzyl)-hydrazide as colourless tarr.

¹H-NMR (CDCl₃, 300 MHz): 3.56 (s, 3H, OMe), 3.63 (s, 3H, OMe), 3.71 (d,2H, CH₂N), 4.73 (s, 1H, CHOH), 6.55-6.19 (m, 7H, ar).

d) A 80% propargyl bromide solution in toluene (2.1 g, 14.5 mmol) isadded slowly at room temperature to a mixture ofhydroxy-(4-methoxy-phenyl)-acetic acidN′-(4-hydroxy-3-methoxy-benzyl)-hydrazide (4.0 g, 12 mmol), 30% sodiumhydroxide solution (3.5 ml, 14.5 mmol) and catalytic amounts oftetrabutylammonium bromide in 35 ml of dichloromethane. The reaction isstirred for 16 hours at +40° C. Subsequently the mixture is evaporatedand the residue is diluted with water and dichloromethane. The phasesare separated and the aqueous phase is extracted three times withdichloromethane. The combined organic phase is washed with brine, driedover sodium sulfate and evaporated. The remaining oil is purified bychromatography on silica gel (ethyl acetate/hexane 7:3) to obtainhydroxy-(4-methoxy-phenyl)-acetic acidN′-(3-methoxy-4-prop-2-ynyloxy-benzyl)-hydrazide.

¹H-NMR (CDCl₃, 300 MHz): 2.35 (dt, 1H, C≡CH), 3.79 (s, 3H, OMe), 3.82(s, 3H, OMe), 3.91 (d, 2H, CH₂N), 4.78 (d, 2H, OCH₂C≡C), 4.93 (s, 1H,CHOH), 6.70-7.26 (m, 7H, ar).

According to the example A2.1 described above the compounds listed intable A2 are obtained. TABLE A2

physico- chemical No. R₁ R₈ data A2.01 H

Oil A2.02 CH₃—CH₂—

Oil A2.03 H

Oil A2.04 CH₃—CH₂—

Oil A2.05 H

Oil A2.06 CH₃—CH₂—

Oil A2.07 H

Oil A2.08 CH₃—CH₂—

Oil

Analogously to the above examples the compounds of tables 1 to 30 areobtained. Ph stands for phenyl TABLE 1 Compounds represented by theFormula I.1 (I.1)

wherein the combination of the groups R₅ R₆, R₉, R₁₀, R₁₁ and Xcorresponds each to one row in table A. TABLE 2 Compounds represented bythe Formula I.2 (I.2)

wherein the combination of the groups R₅, R₆, R₉, R₁₀, R₁₁, and Xcorresponds each to one row in table A. TABLE 3 Compounds represented bythe Formula I.3 (I.3)

wherein the combination of the groups R₅, R₆, R₉, R₁₀, R₁₁ and Xcorresponds each to one row in table A. TABLE 4 Compounds represented bythe Formula I.4 (I.4)

wherein the combination of the groups R₅, R₆, R₉, R₁₀, R₁₁ and Xcorresponds each to one row in table A. TABLE 5 Compounds represented bythe Formula I.5 (I.5)

wherein the combination of the groups R₅, R₆, R₉, R₁₀, R₁₁ and Xcorresponds each to one row in table A. TABLE 6 Compounds represented bythe Formula I.6 (I.6)

wherein the combination of the groups R₅, R₆, R₉, R₁₀, R₁₁, and Xcorresponds each to one row in table A. TABLE 7 Compounds represented bythe Formula I.7 (I.7)

wherein the combination of the groups R₅, R₆, R₉, R₁₀, R₁₁ and Xcorresponds each to one row in table A. TABLE 8 Compounds represented bythe Formula I.8 (I.8)

wherein the combination of the groups R₅, R₆, R₉, R₁₀, R₁₁ and Xcorresponds each to one row in table A. TABLE 9 Compounds represented bythe Formula I.9 (I.9)

wherein the combination of the groups R₅ R₆, R₉, R₁₀, R₁₁ and Xcorresponds each to one table A. TABLE 10 Compounds represented by theFormula I.10 (I.10)

wherein the combination of the groups R₅, R₆, R₉, R₁₀, R₁₁ and Xcorresponds each to one table A. TABLE A (Ph stands for phenyl): No. R₅R₆ X R₉ R₁₀ R₁₁ 001 H H O Ph H H 002 H H O Ph H CH₃ 003 H H O Ph HCH₂CH₃ 004 H H O Ph H CH₂C≡CH 005 CH₃ H O Ph H CH₂C≡CH 006 H H O Ph CH₃CH₂C≡CH 007 H H NH Ph H H 008 H H NH Ph H CH₃ 009 H H NH Ph H CH₂CH₃ 010H H NH Ph H CH₂C≡CH 011 CH₃ H NH Ph H CH₂C≡CH 012 H H NH Ph CH₃ CH₂C≡CH013 H H NCH₃ Ph H H 014 H H NCH₃ Ph H CH₃ 015 H H NCH₃ Ph H CH₂CH₃ 016 HH NCH₃ Ph H CH₂C≡CH 017 CH₃ H NCH₃ Ph H CH₂C≡CH 018 H H N0H3 Ph CH₃CH₂C≡CH 019 H H O 4-F—Ph H H 020 H H O 4-F—Ph H CH₃ 021 H H O 4-F—Ph HCH₂CH₃ 022 H H O 4-F—Ph H CH₂C≡CH 023 CH₃ H O 4-F—Ph H CH₂C≡CH 024 H H O4-F—Ph CH₃ CH₂C≡CH 025 H H NH 4-F—Ph H H 026 H H NH 4-F—Ph H CH₃ 027 H HNH 4-F—Ph H CH₂CH₃ 028 H H NH 4-F—Ph H CH₂C≡CH 029 CH₃ H NH 4-F—Ph HCH₂C≡CH 030 H H NH 4-F—Ph CH₃ CH₂C≡CH 031 H H NCH₃ 4-F—Ph H H 032 H HNCH₃ 4-F—Ph H CH₃ 033 H H NCH₃ 4-F—Ph H CH₂CH₃ 034 H H NCH₃ 4-F—Ph HCH₂C≡CH 035 CH₃ H NCH₃ 4-F—Ph H CH₂C≡CH 036 H H NCH₃ 4-F—Ph CH₃ CH₂C≡CH037 H H O 4-Cl—Ph H H 038 H H O 4-Cl—Ph H CH₃ 039 H H O 4-Cl—Ph H CH₂CH₃040 H H O 4-Cl—Ph H CH₂C≡CH 041 CH₃ H O 4-Cl—Ph H CH₂C≡CH 042 H H O4-Cl—Ph CH₃ CH₂C≡CH 043 H H NH 4-Cl—Ph H H 044 H H NH 4-Cl—Ph H CH₃ 045H H NH 4-Cl—Ph H CH₂CH₃ 046 H H NH 4-Cl—Ph H CH₂C≡CH 047 CH₃ H NH4-Cl—Ph H CH₂C≡CH 048 H H NH 4-Cl—Ph CH₃ CH₂C≡CH 049 H H NCH₃ 4-Cl—Ph HH 050 H H NCH₃ 4-Cl—Ph H CH₃ 051 H H NCH₃ 4-Cl—Ph H CH₂CH₃ 052 H H NCH₃4-Cl—Ph H CH₂C≡CH 053 CH₃ H NCH₃ 4-Cl—Ph H CH₂C≡CH 054 H H NCH₃ 4-Br—PhCH₃ CH₂C≡CH 055 H H O 4-Br—Ph H H 056 H H O 4-Br—Ph H CH₃ 057 H H O4-Br—Ph H CH₂CH₃ 058 H H O 4-Br—Ph H CH₂C≡CH 059 CH₃ H O 4-Br—Ph HCH₂C≡CH 060 H H O 4-Br—Ph CH₃ CH₂C≡CH 061 H H NH 4-Br—Ph H H 062 H H NH4-Br—Ph H CH₃ 063 H H NH 4-Br—Ph H CH₂CH₃ 064 H H NH 4-Br—Ph H CH₂C≡CH065 CH₃ H NH 4-Br—Ph H CH₂C≡CH 066 H H NH 4-Br—Ph CH₃ CH₂C≡CH 067 H HNCH₃ 4-Br—Ph H H 068 H H NCH₃ 4-Br—Ph H CH₃ 069 H H NCH₃ 4-Br—Ph HCH₂CH₃ 070 H H NCH₃ 4-Br—Ph H CH₂C≡CH 071 CH₃ H NCH₃ 4-Br—Ph H CH₂C≡CH072 H H NCH₃ 4-Br—Ph CH₃ CH₂C≡CH 073 H H O 4-CH₃—Ph H H 074 H H O4-CH₃—Ph H CH₃ 075 H H O 4-CH₃—Ph H CH₂CH₃ 076 H H O 4-CH₃—Ph H CH₂C≡CH077 CH₃ H O 4-CH₃—Ph H CH₂C≡CH 078 H H O 4-CH₃—Ph CH₃ CH₂C≡CH 079 H H NH4-CH₃—Ph H H 080 H H NH 4-CH₃—Ph H CH₃ 081 H H NH 4-CH₃—Ph H CH₂CH₃ 082H H NH 4-CH₃—Ph H CH₂C≡CH 083 CH₃ H NH 4-CH₃—Ph H CH₂C≡CH 084 H H NH4-CH₃—Ph CH₃ CH₂C≡CH 085 H H NCH₃ 4-CH₃—Ph H H 086 H H NCH₃ 4-CH₃—Ph HCH₃ 087 H H NCH₃ 4-CH₃—Ph H CH₂CH₃ 088 H H NCH₃ 4-CH₃—Ph H CH₂C≡CH 089CH₃ H NCH₃ 4-CH₃—Ph H CH₂C≡CH 090 H H NCH₃ 4-CH₃—Ph CH₃ CH₂C≡CH 091 H HO 4-CH₃CH₂—Ph H H 092 H H O 4-CH₃CH₂—Ph H CH₃ 093 H H O 4-CH₃CH₂—Ph HCH₂CH₃ 094 H H O 4-CH₃CH₂—Ph H CH₂C≡CH 095 CH₃ H O 4-CH₃CH₂—Ph H CH₂C≡CH096 H H O 4-CH₃CH₂—Ph CH₃ CH₂C≡CH 097 H H NH 4-CH₃CH₂—Ph H H 098 H H NH4-CH₃CH₂—Ph H CH₃ 099 H H NH 4-CH₃CH₂—Ph H CH₂CH₃ 100 H H NH 4-CH₃CH₂—PhH CH₂C≡CH 101 CH₃ H NH 4-CH₃CH₂—Ph H CH₂C≡CH 102 H H NH 4-CH₃CH₂—Ph CH₃CH₂C≡CH 103 H H NCH₃ 4-CH₃CH₂—Ph H H 104 H H NCH₃ 4-CH₃CH₂—Ph H CH₃ 105H H NCH₃ 4-CH₃CH₂—Ph H CH₂CH₃ 106 H H NCH₃ 4-CH₃CH₂—Ph H CH₂C≡CH 107 CH₃H NCH₃ 4-CH₃CH₂—Ph H CH₂C≡CH 108 H H NCH₃ 4-CH₃CH₂—Ph CH₃ CH₂C≡CH 109 HH O 4-CF₃—Ph H H 110 H H O 4-CF₃—Ph H CH₃ 111 H H O 4-CF₃—Ph H CH₂CH₃112 H H O 4-CF₃—Ph H CH₂C≡CH 113 CH₃ H O 4-CF₃—Ph H CH₂C≡CH 114 H H O4-CF₃—Ph CH₃ CH₂C≡CH 115 H H NH 4-CF₃—Ph H H 116 H H NH 4-CF₃—Ph H CH₃117 H H NH 4-CF₃—Ph H CH₂CH₃ 118 H H NH 4-CF₃—Ph H CH₂C≡CH 119 CH₃ H NH4-CF₃—Ph H CH₂C≡CH 120 H H NH 4-CF₃—Ph CH₃ CH₂C≡CH 121 H H NCH₃ 4-CF₃—PhH H 122 H H NCH₃ 4-CF₃—Ph H CH₃ 123 H H NCH₃ 4-CF₃—Ph H CH₂CH₃ 124 H HNCH₃ 4-CF₃—Ph H CH₂C≡CH 125 CH₃ H NCH₃ 4-CF₃—Ph H CH₂C≡CH 126 H H NCH₃4-CF₃—Ph CH₃ CH₂C≡CH 127 H H O 4-CH₃O—Ph H H 128 H H O 4-CH₃O—Ph H CH₃129 H H O 4-CH₃O—Ph H CH₂CH₃ 130 H H O 4-CH₃O—Ph H CH₂C≡CH 131 CH₃ H O4-CH₃O—Ph H CH₂C≡CH 132 H H O 4-CH₃O—Ph CH₃ CH₂C≡CH 133 H H NH 4-CH₃O—PhH H 134 H H NH 4-CH₃O—Ph H CH₃ 135 H H NH 4-CH₃O—Ph H CH₂CH₃ 136 H H NH4-CH₃O—Ph H CH₂C≡CH 137 CH₃ H NH 4-CH₃O—Ph H CH₂C≡CH 138 H H NH4-CH₃O—Ph CH₃ CH₂C≡CH 139 H H NCH₃ 4-CH₃O—Ph H H 140 H H NCH₃ 4-CH₃O—PhH CH₃ 141 H H NCH₃ 4-CH₃O—Ph H CH₂CH₃ 142 H H NCH₃ 4-CH₃O—Ph H CH₂C≡CH143 CH₃ H NCH₃ 4-CH₃O—Ph H CH₂C≡CH 144 H H NCH₃ 4-CH₃O—Ph CH₃ CH₂C≡CH145 H H O 4-CF₃O—Ph H H 146 H H O 4-CF₃O—Ph H CH₃ 147 H H O 4-CF₃O—Ph HCH₂CH₃ 148 H H O 4-CF₃O—Ph H CH₂C≡CH 149 CH₃ H O 4-CF₃O—Ph H CH₂C≡CH 150H H O 4-CF₃O—Ph CH₃ CH₂C≡CH 151 H H NH 4-CF₃O—Ph H H 152 H H NH4-CF₃O—Ph H CH₃ 153 H H NH 4-CF₃O—Ph H CH₂CH₃ 154 H H NH 4-CF₃O—Ph HCH₂C≡CH 155 CH₃ H NH 4-CF₃O—Ph H CH₂C≡CH 156 H H NH 4-CF₃O—Ph CH₃CH₂C≡CH 157 H H NCH₃ 4-CF₃O—Ph H H 158 H H NCH₃ 4-CF₃O—Ph H CH₃ 159 H HNCH₃ 4-CF₃O—Ph H CH₂CH₃ 160 H H NCH₃ 4-CF₃O—Ph H CH₂C≡CH 161 CH₃ H NCH₃4-CF₃O—Ph H CH₂C≡CH 162 H H NCH₃ 4-CF₃O—Ph CH₃ CH₂C≡CH 163 H H O3,4-Cl₂—Ph H H 164 H H O 3,4-Cl₂—Ph H CH₃ 165 H H O 3,4-Cl₂—Ph H CH₂CH₃166 H H O 3,4-Cl₂—Ph H CH₂C≡CH 167 CH₃ H O 3,4-Cl₂—Ph H CH₂C≡CH 168 H HO 3,4-Cl₂—Ph CH₃ CH₂C≡CH 169 H H NH 3,4-Cl₂—Ph H H 170 H H NH 3,4-Cl₂—PhH CH₃ 171 H H NH 3,4-Cl₂—Ph H CH₂CH₃ 172 H H NH 3,4-Cl₂—Ph H CH₂C≡CH 173CH₃ H NH 3,4-Cl₂—Ph H CH₂C≡CH 174 H H NH 3,4-Cl₂—Ph CH₃ CH₂C≡CH 175 H HNCH₃ 3,4-Cl₂—Ph H H 176 H H NCH₃ 3,4-Cl₂—Ph H CH₃ 177 H H NCH₃3,4-Cl₂—Ph H CH₂CH₃ 178 H H NCH₃ 3,4-Cl₂—Ph H CH₂C≡CH 179 CH₃ H NCH₃3,4-Cl₂—Ph H CH₂C≡CH 180 H H NCH₃ 3,4-Cl₂—Ph CH₃ CH₂C≡CH 181 H H O3,4-F₂—Ph H H 182 H H O 3,4-F₂—Ph H CH₃ 183 H H O 3,4-F₂—Ph H CH₂CH₃ 184H H O 3,4-F₂—Ph H CH₂C≡CH 185 CH₃ H O 3,4-F₂—Ph H CH₂C≡CH 186 H H O3,4-F₂—Ph CH₃ CH₂C≡CH 187 H H NH 3,4-F₂—Ph H H 188 H H NH 3,4-F₂—Ph HCH₃ 189 H H NH 3,4-F₂—Ph H CH₂CH₃ 190 H H NH 3,4-F₂—Ph H CH₂C≡CH 191 CH₃H NH 3,4-F₂—Ph H CH₂C≡CH 192 H H NH 3,4-F₂—Ph CH₃ CH₂C≡CH 193 H H NCH₃3,4-F₂—Ph H H 194 H H NCH₃ 3,4-F₂—Ph H CH₃ 195 H H NCH₃ 3,4-F₂—Ph HCH₂CH₃ 196 H H NCH₃ 3,4-F₂—Ph H CH₂C≡CH 197 CH₃ H NCH₃ 3,4-F₂—Ph HCH₂C≡CH 198 H H NCH₃ 3,4-F₂—Ph CH₃ CH₂C≡CH 199 H H O 3-Cl-4-F—Ph H H 200H H O 3-Cl-4-F—Ph H CH₃ 201 H H O 3-Cl-4-F—Ph H CH₂CH₃ 202 H H O3-Cl-4-F—Ph H CH₂C≡CH 203 CH₃ H O 3-Cl-4-F—Ph H CH₂C≡CH 204 H H O3-Cl-4-F—Ph CH₃ CH₂C≡CH 205 H H NH 3-Cl-4-F—Ph H H 206 H H NH3-Cl-4-F—Ph H CH₃ 207 H H NH 3-Cl-4-F—Ph H CH₂CH₃ 208 H H NH 3-Cl-4-F—PhH CH₂C≡CH 209 CH₃ H NH 3-Cl-4-F—Ph H CH₂C≡CH 210 H H NH 3-Cl-4-F—Ph CH₃CH₂C≡CH 211 H H NCH₃ 3-Cl-4-F—Ph H H 212 H H NCH₃ 3-Cl-4-F—Ph H CH₃ 213H H NCH₃ 3-Cl-4-F—Ph H CH₂CH₃ 214 H H NCH₃ 3-Cl-4-F—Ph H CH₂C≡CH 215 CH₃H NCH₃ 3-Cl-4-F—Ph H CH₂C≡CH 216 H H NCH₃ 3-Cl-4-F—Ph CH₃ CH₂C≡CH 217 HH O 4-Cl-3-F—Ph H H 218 H H O 4-Cl-3-F—Ph H CH₃ 219 H H O 4-Cl-3-F—Ph HCH₂CH₃ 220 H H O 4-Cl-3-F—Ph H CH₂C≡CH 221 CH₃ H O 4-Cl-3-F—Ph H CH₂C≡CH222 H H O 4-Cl-3-F—Ph CH₃ CH₂C≡CH 223 H H NH 4-Cl-3-F—Ph H H 224 H H NH4-Cl-3-F—Ph H CH₃ 225 H H NH 4-Cl-3-F—Ph H CH₂CH₃ 226 H H NH 4-Cl-3-F—PhH CH₂C≡CH 227 CH₃ H NH 4-Cl-3-F—Ph H CH₂C≡CH 228 H H NH 4-Cl-3-F—Ph CH₃CH₂C≡CH 229 H H NCH₃ 4-Cl-3-F—Ph H H 230 H H NCH₃ 4-Cl-3-F—Ph H CH₃ 231H H NCH₃ 4-Cl-3-F—Ph H CH₂CH₃ 232 H H NCH₃ 4-Cl-3-F—Ph H CH₂C≡CH 233 CH₃H NCH₃ 4-Cl-3-F—Ph H CH₂C≡CH 234 H H NCH₃ 4-Cl-3-F—Ph CH₃ CH₂C≡CH 235 HH O

H H 236 H H O

H CH₃ 237 H H O

H CH₂CH₃ 238 H H O

H CH₂C≡CH 239 CH₃ H O

H CH₂C≡CH 240 H H O

CH₃ CH₂C≡CH 241 H H NH

H H 242 H H NH

H CH₃ 243 H H NH

H CH₂CH₃ 244 H H NH

H CH₂C≡CH 245 CH₃ H NH

H CH₂C≡CH 246 H H NH

CH₃ CH₂C≡CH 247 H H NCH₃

H H 248 H H NCH₃

H CH₃ 249 H H NCH₃

H CH₂CH₃ 250 H H NCH₃

H CH₂C≡CH 251 CH₃ H NCH₃

H CH₂C≡CH 252 H H NCH₃

CH₃ CH₂C≡CH 253 H H O

H H 254 H H O

H CH₃ 255 H H O

H CH₂CH₃ 256 H H O

H CH₂C≡CH 257 CH₃ H O

H CH₂C≡CH 258 H H O

CH₃ CH₂C≡CH 259 H H NH

H H 260 H H NH

H CH₃ 261 H H NH

H CH₂CH₃ 262 H H NH

H CH₂C≡CH 253 CH₃ H NH

H CH₂C≡CH 264 H H NH

CH₃ CH₂C≡CH 265 H H NCH₃

H H 266 H H NCH₃

H CH₃ 267 H H NCH₃

H CH₂CH₃ 268 H H NCH₃

H CH₂C≡CH 269 CH₃ H NCH₃

H CH₂C≡CH 270 H H NCH₃

CH₃ CH₂C≡CH 271 H H O

H H 272 H H O

H CH₃ 273 H H O

H CH₂CH₃ 274 H H O

H CH₂C≡CH 275 CH₃ H O

H CH₂C≡CH 276 H H O

CH₃ CH₂C≡CH 277 H H NH

H H 278 H H NH

H CH₃ 279 H H NH

H CH₂CH₃ 280 H H NH

H CH₂C≡CH 281 CH₃ H NH

H CH₂C≡CH 282 H H NH

CH₃ CH₂C≡CH 283 H H NCH₃

H H 284 H H NCH₃

H CH₃ 285 H H NCH₃

H CH₂CH₃ 286 H H NCH₃

H CH₂C≡CH 287 CH₃ H NCH₃

H CH₂C≡CH 288 H H NCH₃

CH₃ CH₂C≡CH 289 H H O

H H 290 H H O

H CH₃ 291 H H O

H CH₂CH₃ 292 H H O

H CH₂C≡CH 293 CH₃ H O

H CH₂C≡CH 294 H H O

CH₃ CH₂C≡CH 295 H H NH

H H 296 H H NH

H CH₃ 297 H H NH

H CH₂CH₃ 298 H H NH

H CH₂C≡CH 299 CH₃ H NH

H CH₂C≡CH 300 H H NH

CH₃ CH₂C≡CH 301 H H NCH₃

H H 302 H H NCH₃

H CH₃ 303 H H NCH₃

H CH₂CH₃ 304 H H NCH₃

H CH₂C≡CH 305 CH₃ H NCH₃

H CH₂C≡CH 306 H H NCH₃

CH₃ CH₂C≡CH

TABLE 11 Compounds represented by the Formula I.11 (I.11)

wherein the combination of the groups R₅, R₆, R₁₂, R₁₃, R₁₄ and Xcorresponds each to one row in table B. TABLE 12 Compounds representedby the Formula I.12 (I.12)

wherein the combination of the groups R₅, R₆, R₁₂, R₁₃, R₁₄ and Xcorresponds each to one row in table B. TABLE 13 Compounds representedby the Formula I.13 (I.13)

wherein the combination of the groups R₅, R₆, R₁₂, R₁₃, R₁₄ and Xcorresponds each to one row in table B. TABLE 14 Compounds representedby the Formula I.14 (I.14)

wherein the combination of the groups R₅, R₆, R₁₂, R₁₃, R₁₄ and Xcorresponds each to one row in table B. TABLE 15 Compounds representedby the Formula I.15 (I.15)

wherein the combination of the groups R₅, R₆, R₁₂, R₁₃, R₁₄ and Xcorresponds each to one row in table B. TABLE 16 Compounds representedby the Formula I.16 (I.16)

wherein the combination of the groups R₅ R₆, R₁₂, R₁₃, R₁₄ and Xcorresponds each to one row in table B. TABLE 17 Compounds representedby the Formula I.17 (I.17)

wherein the combination of the groups R₅, R₆, R₁₂, R₁₃, R₁₄ and Xcorresponds each to one row in table B. TABLE 18 Compounds representedby the Formula I.18 (I.18)

wherein the combination of the groups R₅, R₆, R₁₂, R₁₃, R₁₄ and Xcorresponds each to one row in table B. TABLE 19 Compounds representedby the Formula I.19 (I.19)

wherein the combination of the groups R₅, R₆, R₁₂, R₁₃, R₁₄ and Xcorresponds each to one row in table B. TABLE 20 Compounds representedby the Formula I.20 (I.20)

wherein the combination of the groups R₅, R₆, R₁₂, R₁₃, R₁₄ and Xcorresponds each to one row in table B. TABLE 21 Compounds representedby the Formula I.21 (I.21)

wherein the combination of the groups R₅, R₆, R₁₂, R₁₃, R₁₄ and Xcorresponds each to one row in table B. TABLE 22 Compounds representedby the Formula I.22 (I.22)

wherein the combination of the groups R₅, R₆, R₁₂, R₁₃, R₁₄ and Xcorresponds each to one row in table B. TABLE 23 Compounds representedby the Formula I.23 (I.23)

wherein the combination of the groups R₅, R₆, R₁₂, R₁₃, R₁₄ and Xcorresponds each to one row in table B. TABLE 24 Compounds representedby the Formula I.24 (I.24)

wherein the combination of the groups R₅, R₆, R₁₂, R₁₃, R₁₄ and Xcorresponds each to one row in table B. TABLE 25 Compounds representedby the Formula I.25 (I.25)

wherein the combination of the groups R₅, R₆, R₁₂, R₁₃, R₁₄ and Xcorresponds each to one row in table B. TABLE 26 Compounds representedby the Formula I.26 (I.26)

wherein the combination of the groups R₅ R₆, R₁₂, R₁₃, R₁₄ and Xcorresponds each to one row in table B. TABLE 27 Compounds representedby the Formula I.27 (I.27)

wherein the combination of the groups R₅, R₆, R₁₂, R₁₃, R₁₄ and Xcorresponds each to one row in table B. TABLE 28 Compounds representedby the Formula I.28 (I.28)

wherein the combination of the groups R₅ R₆, R₁₂, R₁₃, R₁₄ and Xcorresponds each to one row in table B. TABLE 29 Compounds representedby the Formula I.29 (I.29)

wherein the combination of the groups R₅, R₆, R₁₂, R₁₃, R₁₄ and Xcorresponds each to one row in table B. TABLE 30 Compounds representedby the Formula I.30 (I.30)

wherein the combination of the groups R₅, R₆, R₁₂, R₁₃, R₁₄ and Xcorresponds each to one row in table B. TABLE B (Ph stands for phenyl):No. R₅ R₆ X R₁₂ R₁₃ R₁₄ 001 H H O CH₃ H CH₃ 002 H H O CH₃ H CH₂CH₃ 003 HH O CH₃ H N(CH₃)₂ 004 CH₃ H O CH₃ H CH₃ 005 CH₃ H O CH₃ H CH₂CH₃ 006 CH₃H O CH₃ H N(CH₃)₂ 007 H H NH CH₃ H CH₃ 008 H H NH CH₃ H CH₂CH₃ 009 H HNH CH₃ H N(CH₃)₂ 010 CH₃ H NH CH₃ H CH₃ 011 CH₃ H NH CH₃ H CH₂CH₃ 012CH₃ H NH CH₃ H N(CH₃)₂ 013 H H NCH₃ CH₃ H CH₃ 014 H H NCH₃ CH₃ H CH₂CH₃015 H H NCH₃ CH₃ H N(CH₃)₂ 016 CH₃ H NCH₃ CH₃ H CH₃ 017 CH₃ H NCH₃ CH₃ HCH₂CH₃ 018 CH₃ H NCH₃ CH₃ H N(CH₃)₂ 019 H H O CH₂CH₃ H CH₃ 020 H H OCH₂CH₃ H CH₂CH₃ 021 H H O CH2CH₃ H N(CH₃)₂ 022 CH₃ H O CH₂CH₃ H CH₃ 023CH₃ H O CH₂CH₃ H CH₂CH₃ 024 CH₃ H O CH₂CH₃ H N(CH₃)₂ 025 H H NH CH₂CH₃ HCH₃ 026 H H NH CH₂CH₃ H CH₂CH₃ 027 H H NH CH₂CH₃ H N(CH₃)₂ 028 CH₃ H NHCH₂CH₃ H CH₃ 029 CH₃ H NH CH₂CH₃ H CH₂CH₃ 030 CH₃ H NH CH₂CH₃ H N(CH₃)₂031 H H NCH₃ CH₂CH₃ H CH₃ 032 H H NCH₃ CH₂CH₃ H CH₂CH₃ 033 H H NCH₃CH₂CH₃ H N(CH₃)₂ 034 CH₃ H NCH₃ CH₂CH₃ H CH₃ 035 CH₃ H NCH₃ CH₂CH₃ HCH₂CH₃ 036 CH₃ H NCH₃ CH₂CH₃ H N(CH₃)₂ 037 H H O CH₂CH₂CH₃ H CH₃ 038 H HO CH₂CH₂CH₃ H CH₂CH₃ 039 H H O CH₂CH₂CH₃ H N(CH₃)₂ 040 CH₃ H O CH₂CH₂CH₃H CH₃ 041 CH₃ H O CH₂CH₂CH₃ H CH₂CH₃ 042 CH₃ H O CH₂CH₂CH₃ H N(CH₃)₂ 043H H NH CH₂CH₂CH₃ H CH₃ 044 H H NH CH₂CH₂CH₃ H CH₂CH₃ 045 H H NHCH₂CH₂CH₃ H N(CH₃)₂ 046 CH₃ H NH CH₂CH₂CH₃ H CH₃ 047 CH₃ H NH CH₂CH₂CH₃H CH₂CH₃ 048 CH₃ H NH CH₂CH₂CH₃ H N(CH₃)₂ 049 H H NCH₃ CH₂CH₂CH₃ H CH₃050 H H NCH₃ CH₂CH₂CH₃ H CH₂CH₃ 051 H H NCH₃ CH₂CH₂CH₃ H N(CH₃)₂ 052 CH₃H NCH₃ CH₂CH₂CH₃ H CH₃ 053 CH₃ H NCH₃ CH₂CH₂CH₃ H CH₂CH₃ 054 CH₃ H NCH₃CH₂CH₂CH₃ H N(CH₃)₂ 055 H H O CH(CH₃)₂ H CH₃ 056 H H O CH(CH₃)₂ H CH₂CH₃057 H H O CH(CH₃)₂ H N(CH₃)₂ 058 CH₃ H O CH(CH₃)₂ H CH₃ 059 CH₃ H OCH(CH₃)₂ H CH₂CH₃ 060 CH₃ H O CH(CH₃)₂ H N(CH₃)₂ 061 H H NH CH(CH₃)₂ HCH₃ 062 H H NH CH(CH₃)₂ H CH₂CH₃ 063 H H NH CH(CH₃)₂ H N(CH₃)₂ 064 CH₃ HNH CH(CH₃)₂ H CH₃ 065 CH₃ H NH CH(CH₃)₂ H CH₂CH₃ 066 CH₃ H NH CH(CH₃)₂ HN(CH₃)₂ 067 H H NCH₃ CH(CH₃)₂ H CH₃ 068 H H NCH₃ CH(CH₃)₂ H CH₂CH₃ 069 HH NCH₃ CH(CH₃)₂ H N(CH₃)₂ 070 CH₃ H NCH₃ CH(CH₃)₂ H CH₃ 071 CH₃ H NCH₃CH(CH₃)₂ H CH₂CH₃ 072 CH₃ H NCH₃ CH(CH₃)₂ H N(CH₃)₂ 073 H H O C₃H₅-cyclH CH₃ 074 H H O C₃H₅-cycl H CH₂CH₃ 075 H H O C₃H₅-cycl H N(CH₃)₂ 076 CH₃H O C₃H₅-cycl H CH₃ 077 CH₃ H O C₃H₅-cycl H CH₂CH₃ 078 CH₃ H O C₃H₅-cyclH N(CH₃)₂ 079 H H NH C₃H₅-cycl H CH₃ 080 H H NH C₃H₅-cycl H CH₂CH₃ 081 HH NH C₃H₅-cycl H N(CH₃)₂ 082 CH₃ H NH C₃H₅-cycl H CH₃ 083 CH₃ H NHC₃H₅-cycl H CH₂CH₃ 084 CH₃ H NH C₃H₅-cycl H N(CH₃)₂ 085 H H NCH₃C₃H₅-cycl H CH₃ 086 H H NCH₃ C₃H₅-cycl H CH₂CH₃ 087 H H NCH₃ C₃H₅-cycl HN(CH₃)₂ 088 CH₃ H NCH₃ C₃H₅-cycl H CH₃ 089 CH₃ H NCH₃ C₃H₅-cycl H CH₂CH₃090 CH₃ H NCH₃ C₃H₅-cycl H N(CH₃)₂ 091 H H O CHCH₃(CH₂CH₃) H CH₃ 092 H HO CHCH₃(CH₂CH₃) H CH₂CH₃ 093 H H O CHCH₃(CH₂CH₃) H N(CH₃)₂ 094 CH₃ H OCHCH₃(CH₂CH₃) H CH₃ 095 CH₃ H O CHCH₃(CH₂CH₃) H CH₂CH₃ 096 CH₃ H OCHCH₃(CH₂CH₃) H N(CH₃)₂ 097 H H NH CHCH₃(CH₂CH₃) H CH₃ 098 H H NHCHCH₃(CH₂CH₃) H CH₂CH₃ 099 H H NH CHCH₃(CH₂CH₃) H N(CH₃)₂ 100 CH₃ H NHCHCH₃(CH₂CH₃) H CH₃ 101 CH₃ H NH CHCH₃(CH₂CH₃) H CH₂CH₃ 102 CH₃ H NHCHCH₃(CH₂CH₃) H N(CH₃)₂ 103 H H NCH₃ CHCH₃(CH₂CH₃) H CH₃ 104 H H NCH₃CHCH₃(CH₂CH₃) H CH₂CH₃ 105 H H NCH₃ CHCH₃(CH₂CH₃) H N(CH₃)₂ 106 CH₃ HNCH₃ CHCH₃(CH₂CH₃) H CH₃ 107 CH₃ H NCH₃ CHCH₃(CH₂CH₃) H CH₂CH₃ 108 CH₃ HNCH₃ CHCH₃(CH₂CH₃) H N(CH₃)₂ 109 H H O Ph H CH₃ 110 H H O Ph H CH₂CH₃111 H H O Ph H N(CH₃)₂ 112 CH₃ H O Ph H CH₃ 113 CH₃ H O Ph H CH₂CH₃ 114CH₃ H O Ph H N(CH₃)₂ 115 H H NH Ph H CH₃ 116 H H NH Ph H CH₂CH₃ 117 H HNH Ph H N(CH₃)₂ 118 CH₃ H NH Ph H CH₃ 119 CH₃ H NH Ph H CH₂CH₃ 120 CH₃ HNH Ph H N(CH₃)₂ 121 H H NCH₃ Ph H CH₃ 122 H H NCH₃ Ph H CH₂CH₃ 123 H HNCH₃ Ph H N(CH₃)₂ 124 CH₃ H NCH₃ Ph H CH₃ 125 CH₃ H NCH₃ Ph H CH₂CH₃ 126CH₃ H NCH₃ Ph H N(CH₃)₂ 127 H H O 4-CH₃—Ph H CH₃ 128 H H O 4-CH₃—Ph HCH₂CH₃ 129 H H O 4-CH₃—Ph H N(CH₃)₂ 130 CH₃ H O 4-CH₃—Ph H CH₃ 131 CH₃ HO 4-CH₃—Ph H CH₂CH₃ 132 CH₃ H O 4-CH₃—Ph H N(CH₃)₂ 133 H H NH 4-CH₃—Ph HCH₃ 134 H H NH 4-CH₃—Ph H CH₂CH₃ 135 H H NH 4-CH₃—Ph H N(CH₃)₂ 136 CH₃ HNH 4-CH₃—Ph H CH₃ 137 CH₃ H NH 4-CH₃—Ph H CH₂CH₃ 138 CH₃ H NH 4-CH₃—Ph HN(CH₃)₂ 139 H H NCH₃ 4-CH₃—Ph H CH₃ 140 H H NCH₃ 4-CH₃—Ph H CH₂CH₃ 141 HH NCH₃ 4-CH₃—Ph H N(CH₃)₂ 142 CH₃ H NCH₃ 4-CH₃—Ph H CH₃ 143 CH₃ H NCH₃4-CH₃—Ph H CH₂CH₃ 144 CH₃ H NCH₃ 4-CH₃—Ph H N(CH₃)₂ 145 H H O 4-Br—Ph HCH₃ 146 H H O 4-Br—Ph H CH₂CH₃ 147 H H O 4-Br—Ph H N(CH₃)₂ 148 CH₃ H O4-Br—Ph H CH₃ 149 CH₃ H O 4-Br—Ph H CH₂CH₃ 150 CH₃ H O 4-Br—Ph H N(CH₃)₂151 H H NH 4-Br—Ph H CH₃ 152 H H NH 4-Br—Ph H CH₂CH₃ 153 H H NH 4-Br—PhH N(CH₃)₂ 154 CH₃ H NH 4-Br—Ph H CH₃ 155 CH₃ H NH 4-Br—Ph H CH₂CH₃ 156CH₃ H NH 4-Br—Ph H N(CH₃)₂ 157 H H NCH₃ 4-Br—Ph H CH₃ 158 H H NCH₃4-Br—Ph H CH₂CH₃ 159 H H NCH₃ 4-Br—Ph H N(CH₃)₂ 160 CH₃ H NCH₃ 4-Br—Ph HCH₃ 161 CH₃ H NCH₃ 4-Br—Ph H CH₂CH₃ 162 CH₃ H NCH₃ 4-Br—Ph H N(CH₃)₂ 163H H O 4-Cl—Ph H CH₃ 164 H H O 4-Cl—Ph H CH₂CH₃ 165 H H O 4-Cl—Ph HN(CH₃)₂ 166 CH₃ H O 4-Cl—Ph H CH₃ 167 CH₃ H O 4-Cl—Ph H CH₂CH₃ 168 CH₃ HO 4-Cl—Ph H N(CH₃)₂ 169 H H NH 4-Cl—Ph H CH₃ 170 H H NH 4-Cl—Ph H CH₂CH₃171 H H NH 4-Cl—Ph H N(CH₃)₂ 172 CH₃ H NH 4-Cl—Ph H CH₃ 173 CH₃ H NH4-Cl—Ph H CH₂CH₃ 174 CH₃ H NH 4-Cl—Ph H N(CH₃)₂ 175 H H NCH₃ 4-Cl—Ph HCH₃ 176 H H NCH₃ 4-Cl—Ph H CH₂CH₃ 177 H H NCH₃ 4-Cl—Ph H N(CH₃)₂ 178 CH₃H NCH₃ 4-Cl—Ph H CH₃ 179 CH₃ H NCH₃ 4-Cl—Ph H CH₂CH₃ 180 CH₃ H NCH₃4-Cl—Ph H N(CH₃)₂ 181 H H O 3,4-Cl₂—Ph H CH₃ 182 H H O 3,4-Cl₂—Ph HCH₂CH₃ 183 H H O 3,4-Cl₂—Ph H N(CH₃)₂ 184 CH₃ H O 3,4-Cl₂—Ph H CH₃ 185CH₃ H O 3,4-Cl₂—Ph H CH₂CH₃ 186 CH₃ H O 3,4-Cl₂—Ph H N(CH₃)₂ 187 H H NH3,4-Cl₂—Ph H CH₃ 188 H H NH 3,4-Cl₂—Ph H CH₂CH₃ 189 H H NH 3,4-Cl₂—Ph HN(CH₃)₂ 190 CH₃ H NH 3,4-Cl₂—Ph H CH₃ 191 CH₃ H NH 3,4-Cl₂—Ph H CH₂CH₃192 CH₃ H NH 3,4-Cl₂—Ph H N(CH₃)₂ 193 H H NCH₃ 3,4-Cl₂—Ph H CH₃ 194 H HNCH₃ 3,4-Cl₂—Ph H CH₂CH₃ 195 H H NCH₃ 3,4-Cl₂—Ph H N(CH₃)₂ 196 CH₃ HNCH₃ 3,4-Cl₂—Ph H CH₃ 197 CH₃ H NCH₃ 3,4-Cl₂—Ph H CH₂CH₃ 198 CH₃ H NCH₃3,4-Cl₂—Ph H N(CH₃)₂ 199 H H O

H CH₃ 200 H H O

H CH₂CH₃ 201 H H O

H N(CH₃)₂ 202 CH₃ H O

H CH₃ 203 CH₃ H O

H CH₂CH₃ 204 CH₃ H O

H N(CH₃)₂ 205 H H NH

H CH₃ 206 H H NH

H CH₂CH₃ 207 H H NH

H N(CH₃)₂ 208 CH₃ H NH

H CH₃ 209 CH₃ H NH

H CH₂CH₃ 210 CH₃ H NH

H N(CH₃)₂ 211 H H NCH₃

H CH₃ 212 H H NCH₃

H CH₂CH₃ 213 H H NCH₃

H N(CH₃)₂ 214 CH₃ H NCH₃

H CH₃ 215 CH₃ H NCH₃

H CH₂CH₃ 216 CH₃ H NCH₃

H N(CH₃)₂Formulations may be prepared analogously to those described in, forexample, WO 95/30651, which is incorporated by reference in its entiretyfor all useful purposes.Biological ExamplesD-1: Action against Plasmopara viticola (downy mildew) on vines

5 week old grape seedlings cv. Gutedel are treated with the formulatedtest compound in a spray chamber. One day after application grape plantsare inoculated by spraying a sporangia suspension (4×10⁴ sporangia/ml)on the lower leaf side of the test plants. After an incubation period of6 days at +21° C. and 95% r.h. in a greenhouse the disease incidence isassessed.

Compounds of Tables 1 to 30 exhibit a good fungicidal action againstPlasmopara viticola on vines. Compounds 1.004, 1.040, 5.004, 5.037,5.040, 5.091, 23.055 and 23.056 at 200 ppm inhibit fungal infestation inthis test to at least 80%, while under the same conditions untreatedcontrol plants are infected by the phytopathogenic fungi to over 80%.

D-2: Action Against Phytophthora (Late Blight) on Tomato Plants

3 week old tomato plants cv. Roter Gnom are treated with the formulatedtest compound in a spray chamber. Two day after application the plantsare inoculated by spraying a sporangia suspension (2×10⁴ sporangia/ml)on the test plants. After an incubation period of 4 days at +18° C. and95% r.h. in a growth chamber the disease incidence is assessed.Compounds of Tables 1 to 30 exhibit a long-lasting effect against fungusinfestation. Compounds 1.004, 1.040, 1.055, 1.091, 5.004, 5.037, 5.040,5.055, 5.091, 5.163, 23.055, 23.056 and 23.057 at 200 ppm inhibit fungalinfestation in this test to at least 80%, while under the sameconditions untreated control plants are infected by the phytopathogenicfungi to over 80%.

D-3: Action Against Phytophthora (Late Blight) on Potato Plants

5 week old potato plants cv. Bintje are treated with the formulated testcompound in a spray chamber. Two day after application the plants areinoculated by spraying a sporangia suspension (14×10⁴ sporangia/ml) onthe test plants. After an incubation period of 4 days at +18° C. and 95%r.h. in a growth chamber the disease incidence is assessed. Fungalinfestation is effectively controlled with compounds of Tables 1 to 30.Compounds 1.040, 5.004, 5.040 and 23.055 at 200 ppm inhibit fungalinfestation in this test to at least 80%, while under the sameconditions untreated control plants are infected by the phytopathogenicfungi to over 80%.

1. A compound of formula I

including the optical isomers thereof and mixtures of such isomers,wherein R₁ is hydrogen, C₁-C₈-alkyl, C₃-C₈-cycloalkyl, phenyl ornaphthyl; phenyl and naphthyl being optionally substituted by one tothree substituents selected from the group comprising C₁₋C₈-alkyl,C₂-C₈-alkenyl, C₂-C₈-alkynyl, C₁-C₈-haloalkyl, C₁-C₈-alkoxy,C₁-C₈-haloalkoxy, C₁-C₈-alkylthio, C₁-C₈-haloalkylthio,C₁-C₈-alkylsulfonyl, halogen, cyano and nitro; R₂, R₃, R₅, R₆, and R₇are each independently of each other hydrogen or C₁-C₆-alkyl; R₄ isC₁-C₆-alkyl; or X is O or N—R₇; and R₈ is a group

R₉ is phenyl, naphthyl, 1,3-biphenyl or 1,4-biphenyl, each optionallysubstituted by one to three substituents selected from the groupcomprising C₁-C₈-alkyl, C₂-C₈-alkenyl, C₂-C₈-alkynyl, C₁-C₈-haloalkyl,C₁-C₈-alkoxy, C₁-C₈-haloalkoxy, C₁-C₈-alkylthio, C₁-C₈-haloalkylthio,C₁-C₈-alkylsulfonyl, halogen, cyano, nitro and C₁-C₈-alkoxycarbonyl; R₁₀and R₁₁ are each independently hydrogen, C₁-C₈-alkyl, C₁-C₈-haloalkyl,C₃-C₈-alkenyl or C₃-C₈-alkynyl; R₁₂ is C₁-C₈-alkyl, C₃-C₈-cycloalkyl,phenyl or naphthyl; phenyl and naphthyl being optionally substituted byone to three substituents selected from the group comprisingC₁-C₈-alkyl, C₂-C₈-alkenyl, C₂-C₈-alkynyl, C₁-C₈-haloalkyl,C₁-C₈-alkoxy, C₁-C₈-haloalkoxy, C₁-C₈-alkylthio, C₁-C₈-haloalkylthio,C₁-C₈-alkylsulfonyl, aryl, halogen, cyano and nitro R₁₃ is hydrogen,C₁-C₈-alkyl, C₁-C₈-haloalkyl, C₃-C₈-alkenyl or C₃-C₈-alkynyl; and R₁₄ isC₁-C₈-alkyl, C₁-C₈-haloalkyl, C₁-C₈-alkylamino or C₁-C₈-dialkylamino. 2.A compound according to claim 1 wherein R₁₀ is hydrogen or C₁-C₈-alkyl,X is oxygen, R₈ is —C(R₉R₁₀)—OR₁₁ and R₁₁, is hydrogen or C₃-C₈-alkynyl.3. A compound according to claim 1 wherein X is oxygen, R₈ is—C(R₁₂R₁₃)NH—SO₂—R₁₄, and R₁₂ is C₁-C₈-alkyl or branched C₁-C₈-alkyl. 4.A compound of formula I according to claim 1, wherein R₁ is hydrogen,C₁-C₈-alkyl, C₃-C₈-cycloalkyl, phenyl or naphthyl; phenyl and naphthylbeing optionally substituted by one to three substituents selected fromthe group comprising C₁₋C₈-alkyl, C₂-C₈-alkenyl, C₂-C₈-alkynyl,C₁-C₈-haloalkyl, C₁-C₈-alkoxy, C₁-C₈-haloalkoxy, C₁-C₈-alkylthio,C₁-C₈-haloalkylthio, C₁-C₈-alkylsulfonyl, halogen, cyano and nitro; R₄is C₁-C₆-alkyl; or R₈ is a group

R₉ is phenyl, naphthyl, 1,3-biphenyl or 1,4-biphenyl, each optionallysubstituted by one to three substituents selected from the groupcomprising C₁-C₈-alkyl, C₂-C₈-alkenyl, C₂-C₈-alkynyl, C₁-C₈-haloalkyl,C₁-C₈-alkoxy, C₁-C₈-haloalkoxy, C₁-C₈-alkylthio, C₁-C₈-haloalkylthio,C₁-C₈-alkylsulfonyl, halogen, cyano, nitro and C₁-C₈-alkoxycarbonyl;R₁₁, is hydrogen, C₁-C₈-alkyl or C₃-C₈-alkynyl; and R₁₄ is C₁-C₈-alkyl,C₁-C₈-haloalkyl, C₁-C₈-alkylamino or C₁-C₈-dialkylamino.
 5. A compoundof formula I according to claim 1, wherein R₁ is hydrogen, C₁-C₈-alkyl,C₃-C₈-cycloalkyl; and R₂, R₃, R₅ and R₆ are hydrogen; and R₄ isC₁-C₆-alkyl; and R₉ is phenyl, naphthyl, 1,3-biphenyl or 1,4-biphenyl,each optionally substituted by one to three substituents selected fromthe group comprising C₁-C₈-alkyl, C₂-C₈-alkenyl, C₂-C₈-alkynyl,C₁-C₈-haloalkyl, C₁-C₈-alkoxy, C₁-C₈-haloalkoxy, C₁-C₈-alkylthio,C₁-C₈-haloalkylthio, C₁-C₈-alkylsulfonyl, halogen, cyano, nitro andC₁-C₈-alkoxycarbonyl; and R₁₀ is hydrogen or C₁-C₄-alkyl; and R₁₁ ishydrogen, C₁-C₈-alkyl or C₂-C₈-alkynyl; and R₁₂ is C₁-C₈-alkyl,C₃-C₆-cycloalkyl, C₃-C₈-alkenyl, C₃-C₈-alkynyl; phenyl or benzyl whereinthe phenyl and benzyl is optionally substituted by one to threesubstituents selected from the group comprising C₁-C₈-alkyl,C₂-C₈-alkenyl, C₂-C₈-alkynyl, C₁-C₈-haloalkyl, C₁-C₈-alkoxy,C₁-C₈-haloalkoxy, C₁-C₈-alkylthio, C₁-C₈-haloalkylthio,C₁-C₈-alkylsulfonyl, halogen, cyano, nitro and C₁-C₈-alkoxycarbonyl; andR₁₃ is hydrogen or C₁-C₄-alkyl; and R₁₄ is C₁-C₆-alkyl;C₁-C₆-monoalkylamino or C₁-C₆-dialkylamino.
 6. A compound of formula Iaccording to claim 1, wherein R₁ is hydrogen or C₁-C₆-alkyl, and R₂, R₃,R₅ and R₆ are hydrogen; and R₄ is methyl or ethyl; and R₉ is phenyl ornaphthyl each optionally substituted by one to three substituentsselected from the group comprising C₁-C₆-alkyl, C₁-C₆-haloalkyl,C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkylthio, C₁-C₆-haloalkylthio,halogen, cyano, nitro and C₁-C₆-alkoxycarbonyl; and R₁₀ and R₁₃ are eachhydrogen; and R₁₁ is hydrogen or C₂-C₆-alkynyl; and R₁₂ is C₂-C₆-alkylor C₃-C₆-cycloalkyl; and R₁₄ is C₁-C₆-alkyl or C₁-C₆-dialkylamino.
 7. Acompound of formula I according to claim 1 selected from the groupcomprising2-hydroxy-N-(3-methoxy-4-prop-2-ynyloxy-benzyloxy)-2-phenyl-acetamide,N-(3-methoxy-4-prop-2-ynyloxy-benzyloxy)-2-phenyl-2-prop-2-ynyloxy-acetamide,2-hydroxy-N-(3-methoxy-4-pent-2-ynyloxy-benzyloxy)-2-phenyl-acetamide,N-(3-methoxy-4-pent-2-ynyloxy-benzyloxy)-2-phenyl-2-prop-2-ynyloxy-acetamide,2-(4-chloro-phenyl)-2-hydroxy-N-(3-methoxy-4-prop-2-ynyloxy-benzyloxy)-acetamide,2-(4-chloro-phenyl)-N-(3-methoxy-4-prop-2-ynyloxy-benzyloxy)-2-prop-2-ynyloxy-acetamide,2-(4-chloro-phenyl)-2-hydroxy-N-(3-methoxy-4-pent-2-ynyloxy-benzyloxy)-acetamid e,2-(4-chloro-phenyl)-N-(3-methoxy-4-pent-2-ynyloxy-benzyloxy)-2-prop-2-ynyloxy-acetamide,2-(4-bromo-phenyl)-2-hydroxy-N-(3-methoxy-4-prop-2-ynyloxy-benzyloxy)-acetamide,2-(4-bromo-phenyl)—N-(3-methoxy-4-prop-2-ynyloxy-benzyloxy)-2-prop-2-ynyloxy-acetamide,2-(4-bromo-phenyl)-2-hydroxy-N-(3-methoxy-4-pent-2-ynyloxy-benzyloxy)-acetamide,2-(4-bromo-phenyl)—N-(3-methoxy-4-pent-2-ynyloxy-benzyloxy)-2-prop-2-ynyloxy-acetamide,2-(3,4-dichloro-phenyl)-2-hydroxy-N-(3-methoxy-4-prop-2-ynyloxy-benzyloxy)-acetamide,2-(3,4-dichloro-phenyl)-N-(3-methoxy-4-prop-2-ynyloxy-benzyloxy)-2-prop-2-ynyloxy-acetamide,2-(3,4-dichloro-phenyl)-2-hydroxy-N-(3-methoxy-4-pent-2-ynyloxy-benzyloxy)-acetamide,2-(3,4-dichloro-phenyl)—N-(3-methoxy-4-pent-2-ynyloxy-benzyloxy)-2-prop-2-ynyloxy-acetamide,(S)-2-methylsulfonylamino-N-(3-methoxy-4-prop-2-ynyloxy-benzyloxy)-3-methyl-butyramide,(S)-2-methylsuifonylamino-N-(3-methoxy-4-pent-2-ynyloxy-benzyloxy)-3-methyl-butyramide,(S)-N-{4-[3-(4-chloro-phenyl)-prop-2-ynyloxy]-3-methoxy-benzyloxy}-2-methylsulfonylamino-3-methyl-butyramide,(S)-2-ethylsulfonylamino-N-(3-methoxy-4-prop-2-ynyloxy-benzyloxy)-3-methyl-butyramide,(S)-N-{4-[3-(4-chloro-phenyl)-prop-2-ynyloxy]-3-methoxy-benzyloxy}-2-N,N′-dimethylamino-sulfonylamino-3-methyl-butyramide,2-(4-ethyl-phenyl)-2-hydroxy-N-(3-methoxy-4-prop-2-ynyloxy-benzyloxy)-acetamide,2-(4-ethyl-phenyl)-2-hydroxy-N-(3-methoxy-4-pent-2-ynyloxy-benzyloxy)-acetamide,(S)-2-ethylsulfonylamino-N-(3-methoxy-4-pent-2-ynyloxy-benzyloxy)-3-methyl-butyramide,(S)-N-{4-[3-(4-chloro-phenyl)-prop-2-ynyloxy]-3-methoxy-benzyloxy}-2-ethanesulfonylamino-3-methyl-butyramide,hydroxy-phenyl-acetic acidN′-(3-methoxy-4-prop-2-ynyloxy-benzyl)-hydrazide,phenyl-prop-2-ynyloxy-acetic acidN′-(3-methoxy-4-prop-2-ynyloxy-benzyl)-hydrazide, hydroxy-phenyl-aceticacid N′-(3-methoxy-4-pent-2-ynyloxy-benzyl)-hydrazide,phenyl-prop-2-ynyloxy-acetic acidN′-(3-methoxy-4-pent-2-ynyloxy-benzyl)-hydrazide,(4-chloro-phenyl)-hydroxy-acetic acidN′-(3-methoxy-4-prop-2-ynyloxy-benzyl)-hydrazide,(4-chloro-phenyl)-prop-2-ynyloxy-acetic acidN′-(3-methoxy-4-prop-2-ynyloxy-benzyl)-hydrazide,(4-chloro-phenyl)-hydroxy-acetic acidN′-(3-methoxy-4-pent-2-ynyloxy-benzyl)-hydrazide,(4-chloro-phenyl)-prop-2-ynyloxy-acetic acidN′-(3-methoxy-4-pent-2-ynyloxy-benzyl)-hydrazide,(4-bromo-phenyl)-hydroxy-acetic acidN′-(3-methoxy-4-prop-2-ynyloxy-benzyl)-hydrazide,(4-bromo-phenyl)-prop-2-ynyloxy-acetic acidN′-(3-methoxy-4-prop-2-ynyloxy-benzyl)-hydrazide,(4-bromo-phenyl)-hydroxy-acetic acidN′-(3-methoxy-4-pent-2-ynyloxy-benzyl)-hydrazide,(4-bromo-phenyl)-prop-2-ynyloxy-acetic acidN′-(3-methoxy-4-pent-2-ynyloxy-benzyl)-hydrazide,(3,4-dichloro-phenyl)-hydroxy-acetic acidN′-(3-methoxy-4-prop-2-ynyloxy-benzyl)-hydrazide,(3,4-dichloro-phenyl)-prop-2-ynyloxy-acetic acidN′-(3-methoxy-4-prop-2-ynyloxy-benzyl)-hydrazide,(3,4-dichloro-phenyl)-hydroxy-acetic acidN′-(3-methoxy-4-pent-2-ynyloxy-benzyl)-hydrazide,(3,4-dichloro-phenyl)-prop-2-ynyloxy-acetic acidN′-(3-methoxy-4-pent-2-ynyloxy-benzyl)-hydrazide,N-{(S)-1-[N′-(3-methoxy-4-prop-2-ynyloxy-benzyl)-hydrazinocarbonyl]-2-methyl-propyl}-methylsulfonamide,N-{(S)-1-[N′-(3-methoxy-4-pent-2-ynyloxy-benzyl)-hydrazinocarbonyl]-2-methyl-propyl}-methylsulfonamide,N-[(S)-1-(N′-{4-[3-(4-chloro-phenyl)-prop-2-ynyloxy]-3-methoxy-benzyl}-hydrazinocarbonyl)-2-methyl-propyl]-methylsulfonamide,N-{(S)-1-[N′-(3-methoxy-4-prop-2-ynyloxy-benzyl)-hydrazinocarbonyl]-2-methyl-propyl}-ethylsulfonamide,N-{(S)-1-[N′-(3-methoxy-4-pent-2-ynyloxy-benzyl)-hydrazinocarbonyl]-2-methyl-propyl}-ethylsulfonamide,andN-[(S)-1-(N′-{4-[3-(4-chloro-phenyl)-prop-2-ynyloxy]-3-methoxy-benzyl}-hydrazinocarbonyl)-2-methyl-propyl]-ethylsulfonamide.8. A process for the preparation of a compound of formula I according toclaim 1, which comprises a) reacting an acid of formula II or acarboxy-activated derivative of an acid of formula IIHOOC—R₈  (II) wherein R₈ is as defined for formula I with an amine offormula III

wherein R₄, R₅, R₆ and X are as defined for formula I and reacting theintermediate phenol of formula IV

wherein R₄, R₅, R₆, R₈ and X are as defined for formula I with acompound of formula V

wherein R₁, R₂ and R₃ are as defined for formula I and wherein Y is aleaving group; or b) reacting a compound of formula VI

wherein R₁, R₂, R₃, R₄, R₅, R₆ and X are as defined for formula I withan acid of formula II or a carboxy-activated derivative of an acid offormula II; or c) reacting a compound of formula VIII

wherein R₄ and R₅ are as defined for formula I with an acid hydrazide offormula VII

wherein R₈ is as defined for formula I, and hydrating the intermediateacylhydrazone of formula IX

yielding in a compound of formula IVa, wherein R₄, R₅ and R₈ are asdefined for formula I; or d) reacting a phenol of formula X

wherein R₄, R₅ and R₆ are as defined for formula I, with a compound offormula V as defined above, and transforming the intermediate alcohol offormula XI

wherein R₁, R₂, R₃, R₄, R₅ and R₆ are as defined for formula I, into acompound of formula XII,

wherein R₁, R₂, R₃, R₄, R₅ and R₆ are as defined for formula I andwherein Y is a leaving group like a halide such as a chloride or bromideor a sulfonic ester such as a tosylate, mesylate or triflate, andreacting the compound of formula XII with a compound of formula XIII

wherein R₁₅ and R₁₆ are hydrogen, halogen, methyl or part of anannelated benzene ring to yield an N-alkoxyimide of formula XIV

wherein R₁, R₂, R₃, R₄, R₅ and R₆ are as defined for formula I and R₁₅and R₁₆ are as defined for formula XIII, and reacting the n-alkoxyimideof formula XIV with an amine derivative, like methylamine or butylamineor a hydrazine derivative, such as hydrazine, hydrazine hydrate ormethylhydrazine to yield a compound of formula VIa

wherein R₁, R₂, R₃, R₄, R₅ and R₆ are as defined for formula I.
 9. Acomposition for controlling and protecting against phytopathogenicmicroorganisms, comprising a compound of formula I according to claim 1as active ingredient together with a suitable carrier.
 10. (canceled)11. A method of controlling and preventing an infestation of crop plantsby phytopathogenic microorganisms, which comprises the application of acompound of formula I according to claim 1 as active ingredient to theplant, to parts of plants or to the locus thereof.
 12. A methodaccording to claim 11, wherein the phytopathogenic microorganisms arefungal organisms.
 13. A method of controlling and preventing aninfestation of crop plants by phytopathogenic microorganisms, whichcomprises the application of a composition according to claim 9 toplant, to parts of plants or to the locus thereof.
 14. A methodaccording to claim 13, wherein the phytopathogenic microorganisms arefungal organisms.